diff --git a/src/anharmonic_free_energy/Makefile b/src/anharmonic_free_energy/Makefile index 2eeeeee8..f1877a4b 100644 --- a/src/anharmonic_free_energy/Makefile +++ b/src/anharmonic_free_energy/Makefile @@ -3,7 +3,7 @@ CODE=anharmonic_free_energy PROG=../../build/$(CODE)/$(CODE) OBJECT_PATH=../../build/$(CODE)/ -OBJS = $(OBJECT_PATH)main.o $(OBJECT_PATH)options.o $(OBJECT_PATH)energy.o $(OBJECT_PATH)epot.o +OBJS = $(OBJECT_PATH)main.o $(OBJECT_PATH)lo_thermodynamic_helpers.o $(OBJECT_PATH)options.o $(OBJECT_PATH)thirdorder.o $(OBJECT_PATH)fourthorder.o $(OBJECT_PATH)epot.o LPATH = -L../../lib $(blaslapackLPATH) $(incLPATHhdf) $(incLPATHmpi) IPATH = -I../../inc/libolle -I../../inc/libflap $(blaslapackIPATH) $(incIPATHhdf) $(incIPATHmpi) @@ -24,12 +24,15 @@ clean: .f90.o: $(F90) $(F90FLAGS) -c $< $(LIBS) -$(OBJECT_PATH)main.o: main.f90 $(OBJECT_PATH)options.o $(OBJECT_PATH)energy.o $(OBJECT_PATH)epot.o +$(OBJECT_PATH)main.o: main.f90 $(OBJECT_PATH)options.o $(OBJECT_PATH)lo_thermodynamic_helpers.o $(OBJECT_PATH)thirdorder.o $(OBJECT_PATH)fourthorder.o $(OBJECT_PATH)epot.o $(F90) $(F90FLAGS) -c main.f90 $(LIBS) -o $@ -$(OBJECT_PATH)energy.o: $(OBJECT_PATH)options.o - $(F90) $(F90FLAGS) -c energy.f90 $(LIBS) -o $@ +$(OBJECT_PATH)thirdorder.o: $(OBJECT_PATH)options.o $(OBJECT_PATH)lo_thermodynamic_helpers.o + $(F90) $(F90FLAGS) -c thirdorder.f90 $(LIBS) -o $@ +$(OBJECT_PATH)fourthorder.o: $(OBJECT_PATH)options.o + $(F90) $(F90FLAGS) -c fourthorder.f90 $(LIBS) -o $@ $(OBJECT_PATH)options.o: $(F90) $(F90FLAGS) -c options.f90 $(LIBS) -o $@ -$(OBJECT_PATH)epot.o: epot.f90 +$(OBJECT_PATH)epot.o: epot.f90 $(OBJECT_PATH)lo_thermodynamic_helpers.o $(F90) $(F90FLAGS) -c epot.f90 $(LIBS) -o $@ - +$(OBJECT_PATH)lo_thermodynamic_helpers.o: lo_thermodynamic_helpers.f90 + $(F90) $(F90FLAGS) -c lo_thermodynamic_helpers.f90 $(LIBS) -o $@ diff --git a/src/anharmonic_free_energy/energy.f90 b/src/anharmonic_free_energy/energy.f90 deleted file mode 100644 index c3b502d2..00000000 --- a/src/anharmonic_free_energy/energy.f90 +++ /dev/null @@ -1,1154 +0,0 @@ -module energy -!! get the anharmonic free energy -use konstanter, only: r8, i8, lo_twopi, lo_freqtol, lo_imag, lo_sqtol, lo_status, lo_kb_Hartree -use gottochblandat, only: lo_stop_gracefully, tochar, walltime, lo_chop, lo_trueNtimes, & - lo_progressbar_init, lo_progressbar, lo_planck, lo_trapezoid_integration, open_file, & - lo_flattentensor, lo_sqnorm, lo_linspace, lo_mean, lo_clean_fractional_coordinates -use mpi_wrappers, only: lo_mpi_helper, MPI_DOUBLE_PRECISION, MPI_SUM, MPI_DOUBLE_COMPLEX, MPI_IN_PLACE -use lo_memtracker, only: lo_mem_helper -use type_crystalstructure, only: lo_crystalstructure -use type_forceconstant_secondorder, only: lo_forceconstant_secondorder -use type_forceconstant_thirdorder, only: lo_forceconstant_thirdorder -use type_forceconstant_fourthorder, only: lo_forceconstant_fourthorder -use type_qpointmesh, only: lo_fft_mesh -use type_phonon_dispersions, only: lo_phonon_dispersions - -implicit none -private - -public :: perturbative_anharmonic_free_energy - -contains - -!> Calculates the anharmonic contributions to the free energy -subroutine perturbative_anharmonic_free_energy(p, fct, fcf, qp, dr, temperature, free_energy_thirdorder, free_energy_fourthorder, & - fourthorder, quantum, mw, mem, verbosity) - !> crystal structure - type(lo_crystalstructure), intent(in) :: p - !> third order force constant - type(lo_forceconstant_thirdorder), intent(in) :: fct - !> fourth order force constant - type(lo_forceconstant_fourthorder), intent(in) :: fcf - !> q-point mesh - type(lo_fft_mesh), intent(in) :: qp - !> dispersions - type(lo_phonon_dispersions), intent(in) :: dr - !> temperature - real(r8) :: temperature - !> free energies - real(r8), intent(out) :: free_energy_thirdorder, free_energy_fourthorder - !> what to compute - logical, intent(in) :: quantum, fourthorder - !> mpi helper - type(lo_mpi_helper), intent(inout) :: mw - !> memory tracker - type(lo_mem_helper), intent(inout) :: mem - !> talk a lot? - integer, intent(in) :: verbosity - - complex(r8), dimension(:, :, :), allocatable :: nuvec1, nuvec2 - real(r8), dimension(:, :), allocatable :: en3, en4 - real(r8) :: t0, t1, timer - - ! Start timers - timer = walltime() - t0 = timer - t1 = timer - - ! Set basic things - init: block - real(r8) :: f0, f1 - integer :: iq, imode, ctr, iatom, ix, ialpha - - if (verbosity .gt. 0) then - write (*, *) '' - write (*, *) 'CALCULATING ANHARMONIC FREE ENERGY' - end if - - ! Get the scaled eigenvectors - call mem%allocate(nuvec1, [dr%n_mode, dr%n_mode, qp%n_irr_point], persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%allocate(nuvec2, [dr%n_mode, dr%n_mode, qp%n_full_point], persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - nuvec1 = 0.0_r8 - nuvec2 = 0.0_r8 - - ctr = 0 - do iq = 1, qp%n_irr_point - do imode = 1, dr%n_mode - ctr = ctr + 1 - if (mod(ctr, mw%n) .ne. mw%r) cycle - if (dr%iq(iq)%omega(imode) .gt. lo_freqtol) then - f0 = 1.0_r8/sqrt(dr%iq(iq)%omega(imode)) - else - f0 = 0.0_r8 - end if - do iatom = 1, p%na - f1 = p%invsqrtmass(iatom) - do ix = 1, 3 - ialpha = (iatom - 1)*3 + ix - nuvec1(ialpha, imode, iq) = dr%iq(iq)%egv(ialpha, imode)*f0*f1 - end do - end do - end do - end do - do iq = 1, qp%n_full_point - do imode = 1, dr%n_mode - ctr = ctr + 1 - if (mod(ctr, mw%n) .ne. mw%r) cycle - if (dr%aq(iq)%omega(imode) .gt. lo_freqtol) then - f0 = 1.0_r8/sqrt(dr%aq(iq)%omega(imode)) - else - f0 = 0.0_r8 - end if - do iatom = 1, p%na - f1 = p%invsqrtmass(iatom) - do ix = 1, 3 - ialpha = (iatom - 1)*3 + ix - nuvec2(ialpha, imode, iq) = dr%aq(iq)%egv(ialpha, imode)*f0*f1 - end do - end do - end do - end do - call mw%allreduce('sum', nuvec1) - call mw%allreduce('sum', nuvec2) - - ! Space for free energies per mode - call mem%allocate(en3, [dr%n_mode, qp%n_irr_point], persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%allocate(en4, [dr%n_mode, qp%n_irr_point], persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - en3 = 0.0_r8 - en4 = 0.0_r8 - - if (verbosity .gt. 0) then - t1 = walltime() - write (*, *) '... scaled vectors and made space (', tochar(t1 - t0), 's)' - t0 = t1 - end if - end block init - - ! Integrate out the free energy - third: block - real(r8), external :: zdotu - real(r8), parameter :: threephonon_prefactor = -1.0_r8/48.0_r8 - real(r8), parameter :: fourphonon_prefactor = 1.0_r8/32.0_r8 - real(r8), parameter :: onethird = 1.0_r8/3.0_r8 - complex(r8), dimension(:, :), allocatable :: buf_ev1, buf_ev2, buf_ev3 - complex(r8), dimension(:), allocatable :: evp1, evp2, evp3, ptf - complex(r8) :: c0 - real(r8), dimension(3) :: qv1, qv2, qv3 - real(r8) :: psisq, sigma, om1, om2, om3, n1, n2, n3, f1, f2, prefactor, s1, s2, s3 - integer :: ctr, b1, b2, b3, q1, q2, q3 - - ! Space for intermediate products - call mem%allocate(evp1, dr%n_mode**2, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%allocate(evp2, dr%n_mode**3, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%allocate(ptf, dr%n_mode**3, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%allocate(buf_ev1, [dr%n_mode, dr%n_mode], persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%allocate(buf_ev2, [dr%n_mode, dr%n_mode], persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%allocate(buf_ev3, [dr%n_mode, dr%n_mode], persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - !call mem%allocate(buf_ev4,[dr%n_mode,dr%n_mode],persistent=.false.,scalable=.false.,file=__FILE__,line=__LINE__) - evp1 = 0.0_r8 - evp2 = 0.0_r8 - ptf = 0.0_r8 - buf_ev1 = 0.0_r8 - buf_ev2 = 0.0_r8 - buf_ev3 = 0.0_r8 - !buf_ev4=0.0_r8 - - ! Optimizations: - ! 1) check the prefactors, can maybe do those before in a neater way - ! 2) only have to go over half the q-vectors I think. - if (verbosity .gt. 0) call lo_progressbar_init() - en3 = 0.0_r8 - ctr = 0 - do q1 = 1, qp%n_irr_point - do q2 = 1, qp%n_full_point - ! make it parallel - ctr = ctr + 1 - if (mod(ctr, mw%n) .ne. mw%r) cycle - ! locate third q-vector - q3 = fft_third_grid_index(qp%ip(q1)%full_index, q2, qp%griddensity) - - qv1 = qp%ip(q1)%r - qv2 = qp%ap(q2)%r - qv3 = qp%ap(q3)%r - - prefactor = threephonon_prefactor*qp%ap(q2)%integration_weight - - ! pre-transform the matrix element - call pretransform_phi3(fct, qv2, qv3, ptf) - ! pre-fetch eigenvectors. Maybe a speedup, dunno. - buf_ev1 = nuvec1(:, :, q1) - buf_ev2 = nuvec2(:, :, q2) - buf_ev3 = nuvec2(:, :, q3) - - do b1 = 1, dr%n_mode - do b2 = 1, dr%n_mode - evp1 = 0.0_r8 - call zgeru(dr%n_mode, dr%n_mode, (1.0_r8, 0.0_r8), buf_ev2(:, b2), 1, buf_ev1(:, b1), 1, evp1, dr%n_mode) - do b3 = 1, dr%n_mode - evp2 = 0.0_r8 - call zgeru(dr%n_mode, dr%n_mode*dr%n_mode, (1.0_r8, 0.0_r8), buf_ev3(:, b3), 1, evp1, 1, evp2, dr%n_mode) - evp2 = conjg(evp2) - c0 = dot_product(evp2, ptf) - !c0=zdotu(dr%n_mode**3,evp2,1,ptf,1) - ! And now we have the matrix element. - psisq = real(conjg(c0)*c0, r8) - ! Get a smearing parameter - s1 = dr%default_smearing(b1) - s2 = dr%default_smearing(b2) - s3 = dr%default_smearing(b3) - sigma = sqrt(s1**2 + s2**2 + s3**2) - ! Same sigma as the usual case for debugging. - !sigma=lo_mean(dr%default_smearing) - om1 = dr%iq(q1)%omega(b1) - om2 = dr%aq(q2)%omega(b2) - om3 = dr%aq(q3)%omega(b3) - if (om1 .lt. lo_freqtol) cycle - if (om2 .lt. lo_freqtol) cycle - if (om3 .lt. lo_freqtol) cycle - ! Decide if we take the classical limit for the occupations - if (quantum) then - n1 = lo_planck(temperature, om1) - n2 = lo_planck(temperature, om2) - n3 = lo_planck(temperature, om3) - - ! This is the Wallace expression - ! f1=n1*n2+n1+onethird - ! f1=3*f1*real(1.0_r8/( om1+om2+om3+lo_imag*sigma )) - ! f2=2*n1*n3-n1*n2+n3 - ! f2=3*f2*real(1.0_r8/( om1+om2-om3+lo_imag*sigma )) - ! en3(b1,q1)=en3(b1,q1)+( (f1+f2)*psisq )*prefactor - - ! Try the Cowley expression instead? - else - n1 = lo_kb_Hartree*temperature/om1 - n2 = lo_kb_Hartree*temperature/om2 - n3 = lo_kb_Hartree*temperature/om3 - end if - f1 = (n1 + 1)*(n2 + n3 + 1) + n2*n3 - f2 = n1*n2 + n1*n3 - n2*n3 + 1 - f2 = 3*f2*real(1.0_r8/(om1 + om2 - om3 + lo_imag*sigma)) - f1 = f1*real(1.0_r8/(om1 + om2 + om3 + lo_imag*sigma)) - en3(b1, q1) = en3(b1, q1) + ((f1 + f2)*psisq)*prefactor - end do - end do - end do - end do - if (verbosity .gt. 0 .and. q1 .lt. qp%n_irr_point) then - call lo_progressbar(' ... third order', q1, qp%n_irr_point, walltime() - t0) - end if - end do - - ! Some cleanup - call mem%deallocate(evp1, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%deallocate(evp2, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%deallocate(ptf, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - - if (verbosity .gt. 0) then - t1 = walltime() - call lo_progressbar(' ... third order', qp%n_irr_point, qp%n_irr_point, t1 - t0) - t0 = t1 - end if - call mw%allreduce('sum', en3) - - if (fourthorder) then - ! Do the fourth order? Might as well. - call mem%allocate(evp1, dr%n_mode**2, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%allocate(evp2, dr%n_mode**2, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%allocate(evp3, dr%n_mode**4, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%allocate(ptf, dr%n_mode**4, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - evp1 = 0.0_r8 - evp2 = 0.0_r8 - evp3 = 0.0_r8 - ptf = 0.0_r8 - - if (verbosity .gt. 0) call lo_progressbar_init() - en4 = 0.0_r8 - ctr = 0 - do q1 = 1, qp%n_irr_point - do q2 = 1, qp%n_full_point - ! make it parallel - ctr = ctr + 1 - if (mod(ctr, mw%n) .ne. mw%r) cycle - qv1 = qp%ip(q1)%r - qv2 = qp%ap(q2)%r - prefactor = fourphonon_prefactor*qp%ap(q2)%integration_weight - - ! pre-transform the matrix element - call pretransform_phi4(fcf, qv1, qv2, ptf) - ! pre-fetch eigenvectors. Maybe a speedup, dunno. - buf_ev1 = nuvec1(:, :, q1) - buf_ev2 = nuvec2(:, :, q2) - do b1 = 1, dr%n_mode - do b2 = 1, dr%n_mode - om1 = dr%iq(q1)%omega(b1) - om2 = dr%aq(q2)%omega(b2) - if (om1 .lt. lo_freqtol) cycle - if (om2 .lt. lo_freqtol) cycle - ! Decide if we take the classical limit for the occupations - if (quantum) then - n1 = lo_planck(temperature, om1) - n2 = lo_planck(temperature, om2) - else - n1 = lo_kb_Hartree*temperature/om1 - n2 = lo_kb_Hartree*temperature/om2 - end if - ! Now to get - evp1 = 0.0_r8 - evp2 = 0.0_r8 - evp3 = 0.0_r8 - call zgerc(dr%n_mode, dr%n_mode, (1.0_r8, 0.0_r8), buf_ev1(:, b1), 1, buf_ev1(:, b1), 1, evp1, dr%n_mode) - call zgerc(dr%n_mode, dr%n_mode, (1.0_r8, 0.0_r8), buf_ev2(:, b2), 1, buf_ev2(:, b2), 1, evp2, dr%n_mode) - call zgeru(dr%n_mode**2, dr%n_mode**2, (1.0_r8, 0.0_r8), evp2, 1, evp1, 1, evp3, dr%n_mode**2) - evp3 = conjg(evp3) - psisq = real(dot_product(evp3, ptf), r8) - f1 = (2*n1 + 1)*(2*n2 + 1)*psisq*prefactor - - en4(b1, q1) = en4(b1, q1) + f1 - end do - end do - end do - if (verbosity .gt. 0 .and. q1 .lt. qp%n_irr_point) then - call lo_progressbar(' ... fourth order', q1, qp%n_irr_point, walltime() - t0) - end if - end do - - call mem%deallocate(evp1, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%deallocate(evp2, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%deallocate(evp3, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%deallocate(ptf, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%deallocate(buf_ev1, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%deallocate(buf_ev2, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%deallocate(buf_ev3, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - - if (verbosity .gt. 0) then - t1 = walltime() - call lo_progressbar(' ... fourth order', qp%n_irr_point, qp%n_irr_point, t1 - t0) - t0 = t1 - end if - call mw%allreduce('sum', en4) - end if - end block third - - ! add things up - finalize: block - integer :: q1 - - ! Add it up - free_energy_thirdorder = 0.0_r8 - free_energy_fourthorder = 0.0_r8 - do q1 = 1, qp%n_irr_point - free_energy_thirdorder = free_energy_thirdorder + sum(en3(:, q1))*qp%ip(q1)%integration_weight - if (fourthorder) then - free_energy_fourthorder = free_energy_fourthorder + sum(en4(:, q1))*qp%ip(q1)%integration_weight - end if - end do - ! And normalize it to be per atom - free_energy_thirdorder = free_energy_thirdorder/p%na - free_energy_fourthorder = free_energy_fourthorder/p%na - - ! and cleanup - call mem%deallocate(nuvec1, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%deallocate(nuvec2, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%deallocate(en3, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%deallocate(en4, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - end block finalize - - if (verbosity .gt. 0) then - t1 = walltime() - write (*, *) '... got anharmonic free energy (', tochar(t1 - timer), 's)' - end if - - ! !> and the fourth order things - ! fourth: block - ! real(r8), parameter :: fourphonon_prefactor=1.0_r8/32.0_r8 - ! complex(r8) :: c0 - ! !real(r8), dimension(:,:,:), allocatable :: psibuf - ! real(r8), dimension(4) :: omega - ! real(r8), dimension(3) :: qv1,qv2,qv3,qv4 - ! real(r8) :: psi,prefactor,n1,n2,f1 - ! integer :: q1,q2,b1,b2,b3,i,j,l - ! ! buffers for speed - ! complex(r8), dimension(:,:), allocatable :: egv,flat_cwrk - ! real(r8), dimension(:,:), allocatable :: flat_m,flat_r2,flat_r3,flat_r4 - ! real(r8), dimension(dr%n_mode) :: dumom1,dumom3,dump1,dump3 - ! real(r8) :: omthres - ! integer(i8) :: ctrlong - ! integer, dimension(:,:), allocatable :: flat_ai - ! integer :: nquartet - ! - ! - ! allocate(en4(dr%n_mode,qp%n_irr_point)) - ! en4=0.0_r8 - ! - ! omthres=dr%omega_min*0.5_r8 - ! ! create some buffers - ! nquartet=0 - ! do i=1,fcf%na - ! nquartet=nquartet+fcf%atom(i)%n - ! enddo - ! allocate(flat_m(81,nquartet)) - ! allocate(flat_r2(3,nquartet)) - ! allocate(flat_r3(3,nquartet)) - ! allocate(flat_r4(3,nquartet)) - ! allocate(flat_cwrk(81,fcf%na**4)) - ! allocate(flat_ai(4,nquartet)) - ! l=0 - ! do i=1,fcf%na - ! do j=1,fcf%atom(i)%n - ! l=l+1 - ! flat_r2(:,l)=fcf%atom(i)%quartet(j)%lv2 - ! flat_r3(:,l)=fcf%atom(i)%quartet(j)%lv3 - ! flat_r4(:,l)=fcf%atom(i)%quartet(j)%lv4 - ! flat_m(:,l)=lo_flattentensor( fcf%atom(i)%quartet(j)%mwm ) - ! flat_ai(:,l)=[fcf%atom(i)%quartet(j)%i1,fcf%atom(i)%quartet(j)%i2,fcf%atom(i)%quartet(j)%i3,fcf%atom(i)%quartet(j)%i4] - ! enddo - ! enddo - ! allocate(egv(dr%n_mode,4)) - ! egv=0.0_r8 - ! ! the unit - ! !prefactor=1.0_r8/32.0_r8 - ! - ! ! start integrating - ! ctrlong=0 - ! do q1=1,qp%n_irr_point - ! do q2=1,qp%n_full_point - ! ! q-vectors - ! qv1= qp%ip(q1)%r*lo_twopi - ! qv2=-qp%ip(q1)%r*lo_twopi - ! qv3= qp%ap(q2)%r*lo_twopi - ! qv4=-qp%ap(q2)%r*lo_twopi - ! ! store omega and planck-factors in a buffer - ! do b1=1,dr%n_mode - ! dumom1(b1)=dr%iq(q1)%omega(b1) - ! dumom3(b1)=dr%aq(q2)%omega(b1) - ! dump1(b1)=lo_planck(temperature,dumom1(b1)) - ! dump3(b1)=lo_planck(temperature,dumom3(b1)) - ! enddo - ! - ! prefactor=fourphonon_prefactor*qp%ap(q2)%integration_weight - ! - ! ! technically four band-loops, but b1=b2 and b3=b4 - ! do b1=1,dr%n_mode - ! ctrlong=ctrlong+1; if ( mod(ctrlong,int(mw%n,r8)) .ne. mw%r ) cycle - ! do b3=1,dr%n_mode - ! omega=[dumom1(b1),dumom1(b1),dumom3(b3),dumom3(b3)] - ! if ( minval(omega) .lt. omthres ) cycle - ! egv(:,1)=dr%iq(q1)%egv(:,b1) - ! egv(:,2)=conjg(dr%iq(q1)%egv(:,b1)) - ! egv(:,3)=dr%aq(q2)%egv(:,b3) - ! egv(:,4)=conjg(dr%aq(q2)%egv(:,b3)) - ! call loc_4phpsi(fcf%na,nquartet,flat_r2,flat_r3,flat_r4,flat_m,flat_cwrk,flat_ai,omega,egv,qv2,qv3,qv4,c0) - ! psi=real(c0,r8) - ! - ! n1=dump1(b1) - ! n2=dump3(b3) - ! f1=(2*n1+1)*(2*n2+1)*psi*prefactor - ! - ! - ! en4(b1,q1)=en4(b1,q1)+f1 - ! enddo - ! enddo - ! enddo - ! if ( mw%talk ) write(*,*) 'did',q1,qp%n_irr_point - ! enddo - ! - ! if ( mw%talk ) then - ! write(*,*) 'fourth new:',free_energy_fourthorder - ! endif - ! - ! call mw%allreduce('sum',en4) - ! free_energy_fourthorder=0.0_r8 - ! do q1=1,qp%n_irr_point - ! free_energy_fourthorder=free_energy_fourthorder+sum(en4(:,q1))*qp%ip(q1)%integration_weight - ! enddo - ! free_energy_fourthorder=free_energy_fourthorder/p%na - ! - ! if ( mw%talk ) then - ! write(*,*) 'fourth old:',free_energy_fourthorder - ! endif - ! end block fourth -end subroutine - -!> pre-transform to get half of the third order matrix element -subroutine pretransform_phi3(fct, q2, q3, ptf) - !> third order forceconstant - type(lo_forceconstant_thirdorder), intent(in) :: fct - !> q-vectors - real(r8), dimension(3), intent(in) :: q2, q3 - !> flattened, pretransformed matrix element - complex(r8), dimension(:), intent(out) :: ptf - - integer :: i, j, k, l - - complex(r8) :: expiqr - real(r8), dimension(3) :: rv2, rv3 - real(r8) :: iqr - integer :: a1, a2, a3, ia, ib, ic, t, nb - - nb = fct%na*3 - ptf = 0.0_r8 - do a1 = 1, fct%na - do t = 1, fct%atom(a1)%n - a2 = fct%atom(a1)%triplet(t)%i2 - a3 = fct%atom(a1)%triplet(t)%i3 - - rv2 = fct%atom(a1)%triplet(t)%lv2 - rv3 = fct%atom(a1)%triplet(t)%lv3 - - iqr = dot_product(q2, rv2) + dot_product(q3, rv3) - iqr = -iqr*lo_twopi - expiqr = cmplx(cos(iqr), sin(iqr), r8) - do i = 1, 3 - do j = 1, 3 - do k = 1, 3 - ia = (a1 - 1)*3 + i - ib = (a2 - 1)*3 + j - ic = (a3 - 1)*3 + k - ! Now for the grand flattening scheme, consistent with the zgeru operations above. - l = (ia - 1)*nb*nb + (ib - 1)*nb + ic - ptf(l) = ptf(l) + fct%atom(a1)%triplet(t)%m(i, j, k)*expiqr - end do - end do - end do - end do - end do -end subroutine - -!> pre-transform to get half of the fourth order matrix element -subroutine pretransform_phi4(fcf, q1, q2, ptf) - !> third order forceconstant - type(lo_forceconstant_fourthorder), intent(in) :: fcf - !> q-vectors - real(r8), dimension(3), intent(in) :: q1, q2 - !> flattened, pretransformed matrix element - complex(r8), dimension(:), intent(out) :: ptf - - integer :: i, j, k, l, m - - complex(r8) :: expiqr - real(r8), dimension(3) :: rv2, rv3, rv4 - real(r8) :: iqr - integer :: a1, a2, a3, a4, ia, ib, ic, id, q, nb - - nb = fcf%na*3 - ptf = 0.0_r8 - do a1 = 1, fcf%na - do q = 1, fcf%atom(a1)%n - a2 = fcf%atom(a1)%quartet(q)%i2 - a3 = fcf%atom(a1)%quartet(q)%i3 - a4 = fcf%atom(a1)%quartet(q)%i4 - - rv2 = fcf%atom(a1)%quartet(q)%lv2 - rv3 = fcf%atom(a1)%quartet(q)%lv3 - rv4 = fcf%atom(a1)%quartet(q)%lv4 - - iqr = -dot_product(q1, rv2) + dot_product(q2, rv3) - dot_product(q2, rv4) - iqr = -iqr*lo_twopi - expiqr = cmplx(cos(iqr), sin(iqr), r8) - do l = 1, 3 - do k = 1, 3 - do j = 1, 3 - do i = 1, 3 - ia = (a1 - 1)*3 + i - ib = (a2 - 1)*3 + j - ic = (a3 - 1)*3 + k - id = (a4 - 1)*3 + l - ! Now for the grand flattening scheme, consistent with the zgeru operations above. - m = (ia - 1)*nb*nb*nb + (ib - 1)*nb*nb + (ic - 1)*nb + id - ptf(m) = ptf(m) + fcf%atom(a1)%quartet(q)%m(i, j, k, l)*expiqr - end do - end do - end do - end do - end do - end do -end subroutine - -!> returns the index on the grid that gives q3=-q1-q2 -pure function fft_third_grid_index(i1, i2, dims) result(i3) - !> index to q1 - integer, intent(in) :: i1 - !> index to q2 - integer, intent(in) :: i2 - !> dimensions of the grid - integer, dimension(3), intent(in) :: dims - !> index to q3 - integer :: i3 - - integer, dimension(3) :: gi1, gi2, gi3 - integer :: l, k - - ! Convert triplet to singlet - gi1 = singlet_to_triplet(i1, dims(2), dims(3)) - gi2 = singlet_to_triplet(i2, dims(2), dims(3)) - do l = 1, 3 - gi3(l) = 3 - gi1(l) - gi2(l) - end do - do k = 1, 3 - do l = 1, 3 - if (gi3(l) .lt. 1) gi3(l) = gi3(l) + dims(l) - if (gi3(l) .gt. dims(l)) gi3(l) = gi3(l) - dims(l) - end do - end do - ! convert it back to a singlet - i3 = triplet_to_singlet(gi3, dims(2), dims(3)) - -contains - !> convert a linear index to a triplet - pure function singlet_to_triplet(l, ny, nz) result(gi) - !> linear index - integer, intent(in) :: l - !> second dimension - integer, intent(in) :: ny - !> third dimension - integer, intent(in) :: nz - !> grid-index - integer, dimension(3) :: gi - - integer :: i, j, k - - k = mod(l, nz) - if (k .eq. 0) k = nz - j = mod((l - k)/nz, ny) + 1 - i = (l - k - (j - 1)*nz)/(nz*ny) + 1 - gi = [i, j, k] - end function - !> convert a triplet index to a singlet - pure function triplet_to_singlet(gi, ny, nz) result(l) - !> grid-index - integer, dimension(3), intent(in) :: gi - !> second dimension - integer, intent(in) :: ny - !> third dimension - integer, intent(in) :: nz - !> linear index - integer :: l - - l = (gi(1) - 1)*ny*nz + (gi(2) - 1)*nz + gi(3) - end function -end function - -! subroutine loc_4phpsi(na,nquartet,flv2,flv3,flv4,fm,fcw,fai,omega,egv,q2,q3,q4,psi) -! !> temporary work arrays, that actually is the force constant -! integer, intent(in) :: na,nquartet -! real(r8), dimension(3,nquartet), intent(in) :: flv2,flv3,flv4 -! real(r8), dimension(81,nquartet), intent(in) :: fm -! complex(r8), dimension(81,na*na*na*na), intent(inout) :: fcw -! integer, dimension(4,nquartet), intent(in) :: fai -! !> four frequencies -! real(r8), dimension(4), intent(in) :: omega -! !> four eigenvectors -! complex(r8), dimension(na*3,4), intent(in) :: egv -! !> three q-points -! real(r8), dimension(3), intent(in) :: q2,q3,q4 -! !> the matrix element -! complex(r8), intent(out) :: psi -! -! complex(r8) :: expiqr,c0 -! real(r8), dimension(3) :: rv2,rv3,rv4 -! real(r8) :: iqr,omegaprod -! real(r8), parameter :: enhet=1.0_r8 !5.8104841317859603E074_r8 -! integer :: atom1,atom2,atom3,atom4,i,j,k,l,k1,k2,k3,k4,ii,jj -! integer :: na3,na2 -! -! na3=na*na*na -! na2=na*na -! ! Eigenvector product, again -! do atom1=1,na -! do atom2=1,na -! do atom3=1,na -! do atom4=1,na -! ii=(atom1-1)*na3+(atom2-1)*na2+(atom3-1)*na+atom4 -! do i=1,3 -! do j=1,3 -! do k=1,3 -! do l=1,3 -! jj=(i-1)*27+(j-1)*9+(k-1)*3+l -! k1=(atom1-1)*3+i -! k2=(atom2-1)*3+j -! k3=(atom3-1)*3+k -! k4=(atom4-1)*3+l -! fcw(jj,ii)=egv(k1,1)*egv(k2,2)*egv(k3,3)*egv(k4,4) -! enddo -! enddo -! enddo -! enddo -! enddo -! enddo -! enddo -! enddo -! -! ! Frequency product -! omegaprod=omega(1)*omega(2)*omega(3)*omega(4) -! omegaprod=sqrt(omegaprod) -! ! The actual matrix element -! c0=0.0_r8 -! do i=1,nquartet -! atom1=fai(1,i) -! atom2=fai(2,i) -! atom3=fai(3,i) -! atom4=fai(4,i) -! ii=(atom1-1)*na3+(atom2-1)*na2+(atom3-1)*na+atom4 -! rv2=flv2(:,i) -! rv3=flv3(:,i) -! rv4=flv4(:,i) -! iqr=dot_product(q2,rv2)+dot_product(q3,rv3)+dot_product(q4,rv4) -! expiqr=cmplx(cos(iqr),sin(iqr),r8) -! c0=c0+sum(fcw(:,ii)*fm(:,i))*expiqr -! enddo -! psi=enhet*c0/omegaprod -! end subroutine - -! !> impossibly convoluted way of calculating the anharmonic free energy. Really parallel though! -! subroutine impossible_free_energy(uc,fc,fct,fcf,qp,dr,temperature,free_energy_thirdorder,free_energy_fourthorder,mw) -! !> crystal structure -! type(lo_crystalstructure), intent(in) :: uc -! !> second order force constant -! type(lo_forceconstant_secondorder), intent(inout) :: fc -! !> third order force constant -! type(lo_forceconstant_thirdorder), intent(in) :: fct -! !> fourth order force constant -! type(lo_forceconstant_fourthorder), intent(in) :: fcf -! !> q-point mesh -! type(lo_fft_mesh), intent(in) :: qp -! !> dispersions -! type(lo_phonon_dispersions), intent(in) :: dr -! !> temperature -! real(r8) :: temperature -! !> free energies -! real(r8), intent(out) :: free_energy_thirdorder,free_energy_fourthorder -! !> mpi helper -! type(lo_mpi_helper) :: mw -! -! real(r8), dimension(:,:), allocatable :: en3,en4 -! real(r8) :: omthres,sigma -! integer :: index_gamma -! real(r8) :: t0,t1 -! -! t0=walltime() -! t1=t0 -! -! init: block -! integer :: i -! sigma=lo_mean(dr%default_smearing) -! omthres=dr%omega_min*0.5_r8 -! index_gamma=-1 -! do i=1,qp%n_irr_point -! if ( lo_sqnorm(qp%ip(i)%r) .lt. lo_sqtol ) then -! index_gamma=i -! exit -! endif -! enddo -! lo_allocate(en3(dr%n_mode,qp%n_irr_point)) -! lo_allocate(en4(dr%n_mode,qp%n_irr_point)) -! en3=0.0_r8 -! en4=0.0_r8 -! -! if ( mw%talk ) then -! t1=walltime() -! write(*,*) 'init:',t1-t0 -! t0=t1 -! endif -! end block init -! -! ! Start with the third order -! third: block -! complex(r8) :: c0 -! real(r8), dimension(3) :: v0,qv1,qv2,qv3,omega -! real(r8) :: psisquare,doublepsi,prefactor -! real(r8) :: n1,n2,n3,f0,f1,f2,f3 -! integer, dimension(3) :: gi -! integer :: q1,q2,q3,iq2,b1,b2,b3,ctr -! ! buffers for speed -! complex(r8), dimension(:,:,:,:,:,:), allocatable :: cwrk,cdwrk -! real(r8), dimension(dr%n_mode) :: pbuf1,pbuf2,pbuf3,ombuf1,ombuf2,ombuf3 -! real(r8), parameter :: onethird=1.0_r8/3.0_r8 -! -! ! work-array for the scattering amplitude -! allocate(cwrk(3,3,3,fct%na,fct%na,fct%na)) ! work-array for scattering amplitude -! allocate(cdwrk(3,3,3,fct%na,fct%na,fct%na)) ! work-array for scattering amplitude -! -! ctr=0 -! prefactor=-1.0_r8/48.0_r8 -! do q1=1,qp%n_irr_point -! do q2=1,qp%n_full_point -! ! locate the third q-vector -! v0=uc%cartesian_to_fractional(-qp%ip(q1)%r-qp%ap(q2)%r,reciprocal=.true.) -! gi=qp%index_from_coordinate(v0) -! q3=qp%gridind2ind(gi(1),gi(2),gi(3)) -! ! buffer things -! do b1=1,dr%n_mode -! ombuf1(b1)=dr%iq(q1)%omega(b1) -! ombuf2(b1)=dr%aq(q2)%omega(b1) -! ombuf3(b1)=dr%aq(q3)%omega(b1) -! pbuf1(b1)=lo_planck(temperature,ombuf1(b1)) -! pbuf2(b1)=lo_planck(temperature,ombuf2(b1)) -! pbuf3(b1)=lo_planck(temperature,ombuf3(b1)) -! enddo -! ! get the vectors, and add 2*pi -! qv1=-qp%ip(q1)%r*lo_twopi -! qv2=-qp%ap(q2)%r*lo_twopi -! qv3=-qp%ap(q3)%r*lo_twopi -! ! do the MPI-division here. Should make it really parallel. -! ! should also mean minimal overhead. -! do b1=1,dr%n_mode -! ctr=ctr+1; if ( mod(ctr,mw%n) .ne. mw%r ) cycle -! do b2=1,dr%n_mode -! do b3=1,dr%n_mode -! omega(1)=ombuf1(b1) -! omega(2)=ombuf2(b2) -! omega(3)=ombuf3(b3) -! if ( minval(omega) .gt. omthres ) then -! ! normal three-phonon thing, matrix element -! call loc_3phpsi(fct,omega,dr%iq(q1)%egv(:,b1),dr%aq(q2)%egv(:,b2),dr%aq(q3)%egv(:,b3),qv2,qv3,cwrk,c0) -! psisquare=abs(conjg(c0)*c0) -! n1=pbuf1(b1) -! n2=pbuf2(b2) -! n3=pbuf3(b3) -! ! prefactors for the other stuff -! f1=n1*n2+n1+onethird -! f1=3*f1*real(1.0_r8/( omega(1)+omega(2)+omega(3)+lo_imag*sigma )) -! f2=2*n1*n3-n1*n2+n3 -! f2=3*f2*real(1.0_r8/( omega(1)+omega(2)-omega(3)+lo_imag*sigma )) -! else -! f1=0.0_r8 -! f2=0.0_r8 -! psisquare=0.0_r8 -! endif -! ! get the double-psi term -! !omega(3)=dr%iq(index_gamma)%omega(b3) -! !if ( minval(omega) .gt. omthres ) then -! ! call loc_3phdbl(fct,omega,dr%iq(q1)%egv(:,b1),dr%aq(q2)%egv(:,b2),dr%aq(index_gamma)%egv(:,b3),qv1,qv2,cwrk,cdwrk,c0) -! ! doublepsi=real(c0) -! ! f3=6*(n1*(n2+1)+0.25_r8) -! ! f3=f3*real(1.0_r8/( omega(3)+lo_imag*sigma )) -! !else -! ! doublepsi=0.0_r8 -! ! f3=0.0_r8 -! !endif -! doublepsi=0.0_r8 -! f3=0.0_r8 -! ! Add it up -! !psisquare=1.0_r8 -! f0=( (f1+f2)*psisquare+f3*doublepsi )*prefactor -! en3(b1,q1)=en3(b1,q1)+f0 -! enddo -! enddo -! enddo -! enddo -! enddo -! -! if ( mw%talk ) then -! t1=walltime() -! write(*,*) 'third:',t1-t0 -! t0=t1 -! endif -! -! end block third -! -! !> and the fourth order things -! fourth: block -! complex(r8) :: c0 -! real(r8), dimension(:,:,:), allocatable :: psibuf -! real(r8), dimension(4) :: omega -! real(r8), dimension(3) :: qv1,qv2,qv3,qv4 -! real(r8) :: psi,prefactor,n1,n2,f1 -! integer :: q1,q2,b1,b2,b3,b4,i,j,l -! ! buffers for speed -! complex(r8), dimension(:,:), allocatable :: egv,flat_cwrk -! real(r8), dimension(:,:), allocatable :: flat_m,flat_r2,flat_r3,flat_r4 -! real(r8), dimension(dr%n_mode) :: dumom1,dumom3,dump1,dump3 -! integer(i8) :: ctrlong -! integer, dimension(:,:), allocatable :: flat_ai -! integer :: nquartet -! -! ! create some buffers -! nquartet=0 -! do i=1,fcf%na -! nquartet=nquartet+fcf%atom(i)%n -! enddo -! allocate(flat_m(81,nquartet)) -! allocate(flat_r2(3,nquartet)) -! allocate(flat_r3(3,nquartet)) -! allocate(flat_r4(3,nquartet)) -! allocate(flat_cwrk(81,fcf%na**4)) -! allocate(flat_ai(4,nquartet)) -! l=0 -! do i=1,fcf%na -! do j=1,fcf%atom(i)%n -! l=l+1 -! flat_r2(:,l)=fcf%atom(i)%quartet(j)%lv2 -! flat_r3(:,l)=fcf%atom(i)%quartet(j)%lv3 -! flat_r4(:,l)=fcf%atom(i)%quartet(j)%lv4 -! flat_m(:,l)=lo_flattentensor( fcf%atom(i)%quartet(j)%mwm ) -! flat_ai(:,l)=[fcf%atom(i)%quartet(j)%i1,fcf%atom(i)%quartet(j)%i2,fcf%atom(i)%quartet(j)%i3,fcf%atom(i)%quartet(j)%i4] -! enddo -! enddo -! lo_allocate(egv(dr%n_mode,4)) -! egv=0.0_r8 -! ! the unit -! prefactor=1.0_r8/32.0_r8 -! -! ! start integrating -! ctrlong=0 -! do q1=1,qp%n_irr_point -! do q2=1,qp%n_full_point -! ! q-vectors -! qv1= qp%ip(q1)%r*lo_twopi -! qv2=-qp%ip(q1)%r*lo_twopi -! qv3= qp%ap(q2)%r*lo_twopi -! qv4=-qp%ap(q2)%r*lo_twopi -! ! store omega and planck-factors in a buffer -! do b1=1,dr%n_mode -! dumom1(b1)=dr%iq(q1)%omega(b1) -! dumom3(b1)=dr%aq(q2)%omega(b1) -! dump1(b1)=lo_planck(temperature,dumom1(b1)) -! dump3(b1)=lo_planck(temperature,dumom3(b1)) -! enddo -! ! technically four band-loops, but b1=b2 and b3=b4 -! do b1=1,dr%n_mode -! ctrlong=ctrlong+1; if ( mod(ctrlong,int(mw%n,r8)) .ne. mw%r ) cycle -! do b3=1,dr%n_mode -! omega=[dumom1(b1),dumom1(b1),dumom3(b3),dumom3(b3)] -! if ( minval(omega) .lt. omthres ) cycle -! egv(:,1)=dr%iq(q1)%egv(:,b1) -! egv(:,2)=conjg(dr%iq(q1)%egv(:,b1)) -! egv(:,3)=dr%aq(q2)%egv(:,b3) -! egv(:,4)=conjg(dr%aq(q2)%egv(:,b3)) -! call loc_4phpsi(fcf%na,nquartet,flat_r2,flat_r3,flat_r4,flat_m,flat_cwrk,flat_ai,omega,egv,qv2,qv3,qv4,c0) -! psi=real(c0) -! n1=dump1(b1) -! n2=dump3(b3) -! f1=(2*n1+1)*(2*n2+1)*psi*prefactor -! en4(b1,q1)=en4(b1,q1)+f1 -! enddo -! enddo -! enddo -! enddo -! -! if ( mw%talk ) then -! t1=walltime() -! write(*,*) 'fourth:',t1-t0 -! t0=t1 -! endif -! -! end block fourth -! -! !> add things up -! finalize: block -! integer :: i,j -! call mpi_allreduce(MPI_IN_PLACE,en3,dr%n_mode*qp%n_irr_point,MPI_DOUBLE_PRECISION,MPI_SUM,mw%comm,mw%error ) -! call mpi_allreduce(MPI_IN_PLACE,en4,dr%n_mode*qp%n_irr_point,MPI_DOUBLE_PRECISION,MPI_SUM,mw%comm,mw%error ) -! en3=en3/real(qp%n_full_point,r8)/real(fc%na,r8) -! en4=en4/real(qp%n_full_point,r8)/real(fc%na,r8) -! free_energy_thirdorder=0.0_r8 -! free_energy_fourthorder=0.0_r8 -! do i=1,qp%n_irr_point -! free_energy_thirdorder=free_energy_thirdorder+sum(en3(:,i))*qp%ip(i)%integration_weight -! free_energy_fourthorder=free_energy_fourthorder+sum(en4(:,i))*qp%ip(i)%integration_weight -! enddo -! end block finalize -! -! contains -! ! specialized four-phonon matrix element, where q2=-q1, q4=-q3 -! subroutine loc_4phpsi(na,nquartet,flv2,flv3,flv4,fm,fcw,fai,omega,egv,q2,q3,q4,psi) -! !> temporary work arrays, that actually is the force constant -! integer, intent(in) :: na,nquartet -! real(r8), dimension(3,nquartet), intent(in) :: flv2,flv3,flv4 -! real(r8), dimension(81,nquartet), intent(in) :: fm -! complex(r8), dimension(81,na*na*na*na), intent(inout) :: fcw -! integer, dimension(4,nquartet), intent(in) :: fai -! !> four frequencies -! real(r8), dimension(4), intent(in) :: omega -! !> four eigenvectors -! complex(r8), dimension(na*3,4), intent(in) :: egv -! !> three q-points -! real(r8), dimension(3), intent(in) :: q2,q3,q4 -! !> the matrix element -! complex(r8), intent(out) :: psi -! -! complex(r8) :: expiqr,c0 -! real(r8), dimension(3) :: rv2,rv3,rv4 -! real(r8) :: iqr,omegaprod -! real(r8), parameter :: enhet=1.0_r8 !5.8104841317859603E074_r8 -! integer :: atom1,atom2,atom3,atom4,i,j,k,l,k1,k2,k3,k4,ii,jj -! integer :: na3,na2 -! -! na3=na*na*na -! na2=na*na -! ! Eigenvector product, again -! do atom1=1,na -! do atom2=1,na -! do atom3=1,na -! do atom4=1,na -! ii=(atom1-1)*na3+(atom2-1)*na2+(atom3-1)*na+atom4 -! do i=1,3 -! do j=1,3 -! do k=1,3 -! do l=1,3 -! jj=(i-1)*27+(j-1)*9+(k-1)*3+l -! k1=(atom1-1)*3+i -! k2=(atom2-1)*3+j -! k3=(atom3-1)*3+k -! k4=(atom4-1)*3+l -! fcw(jj,ii)=egv(k1,1)*egv(k2,2)*egv(k3,3)*egv(k4,4) -! enddo -! enddo -! enddo -! enddo -! enddo -! enddo -! enddo -! enddo -! -! ! Frequency product -! omegaprod=omega(1)*omega(2)*omega(3)*omega(4) -! omegaprod=sqrt(omegaprod) -! ! The actual matrix element -! c0=0.0_r8 -! do i=1,nquartet -! atom1=fai(1,i) -! atom2=fai(2,i) -! atom3=fai(3,i) -! atom4=fai(4,i) -! ii=(atom1-1)*na3+(atom2-1)*na2+(atom3-1)*na+atom4 -! rv2=flv2(:,i) -! rv3=flv3(:,i) -! rv4=flv4(:,i) -! iqr=dot_product(q2,rv2)+dot_product(q3,rv3)+dot_product(q4,rv4) -! expiqr=cmplx(cos(iqr),sin(iqr),r8) -! c0=c0+sum(fcw(:,ii)*fm(:,i))*expiqr -! enddo -! psi=enhet*c0/omegaprod -! end subroutine -! !> The three-phonon matrix element -! pure subroutine loc_3phpsi(fc,omega,egv1,egv2,egv3,q2,q3,egvprod,psi) -! !> the third order force constant -! class(lo_forceconstant_thirdorder), intent(in) :: fc -! !> the frequencies in question -! real(r8), dimension(3), intent(in) :: omega -! !> the eigenvectors -! complex(r8), dimension(fc%na*3), intent(in) :: egv1,egv2,egv3 -! !> the two q-vectors that matter -! real(r8), dimension(3), intent(in) :: q2,q3 -! !> work array -! complex(r8), dimension(3,3,3,fc%na,fc%na,fc%na), intent(inout) :: egvprod -! ! Matrix element -! complex(r8), intent(out) :: psi -! -! complex(r8) :: expiqr,c0 -! real(r8), dimension(3) :: rv2,rv3 -! real(r8) :: iqr,omegaprod -! real(r8), parameter :: enhet=1.0_r8 !2.367755374064161E51_r8 -! integer :: atom1,atom2,atom3,i,j,k,k1,k2,k3,t -! -! ! Eigenvector product -! do atom3=1,fc%na -! do atom2=1,fc%na -! do atom1=1,fc%na -! do k=1,3 -! do j=1,3 -! do i=1,3 -! k1=(atom1-1)*3+i -! k2=(atom2-1)*3+j -! k3=(atom3-1)*3+k -! egvprod(i,j,k,atom1,atom2,atom3)=egv1(k1)*egv2(k2)*egv3(k3) -! enddo -! enddo -! enddo -! enddo -! enddo -! enddo -! ! Frequency product -! omegaprod=omega(1)*omega(2)*omega(3) -! omegaprod=sqrt(omegaprod) -! ! The actual matrix element -! c0=0.0_r8 -! do atom1=1,fc%na -! do t=1,fc%atom(atom1)%n -! atom2=fc%atom(atom1)%triplet(t)%i2 -! atom3=fc%atom(atom1)%triplet(t)%i3 -! -! rv2=fc%atom(atom1)%triplet(t)%lv2 -! rv3=fc%atom(atom1)%triplet(t)%lv3 -! -! iqr=dot_product(q2,rv2)+dot_product(q3,rv3) -! expiqr=cmplx(cos(iqr),sin(iqr),r8) -! ! Note that the masses are premultiplied into the forceconstants, much faster. -! c0=c0+sum(fc%atom(atom1)%triplet(t)%mwm*egvprod(:,:,:,atom1,atom2,atom3))*expiqr -! enddo -! enddo -! psi=enhet*c0/omegaprod -! end subroutine -! !> The three-phonon matrix element, but product of two complex thingies -! subroutine loc_3phdbl(fc,omega,egv1,egv2,egv3,q1,q2,egvprod1,egvprod2,doublepsi) -! !> the third order force constant -! class(lo_forceconstant_thirdorder), intent(in) :: fc -! !> the frequencies in question -! real(r8), dimension(3), intent(in) :: omega -! !> the eigenvectors -! complex(r8), dimension(fc%na*3), intent(in) :: egv1,egv2,egv3 -! !> the two q-vectors that matter -! real(r8), dimension(3), intent(in) :: q1,q2 -! !> work arrays -! complex(r8), dimension(3,3,3,fc%na,fc%na,fc%na), intent(inout) :: egvprod1,egvprod2 -! !> double psi -! complex(r8), intent(out) :: doublepsi -! ! -! integer :: atom1,atom2,atom3,i,j,k,k1,k2,k3,t -! complex(r8) :: expiqr,c0,c1 -! real(r8), dimension(3) :: rv2,rv3 -! real(r8), parameter :: enhet=2.367755374064161E51_r8 -! real(r8) :: iqr,omegaprod1,omegaprod2 -! -! ! Not enough room on the stack for large unitcells, have to allocate space -! do atom3=1,fc%na -! do atom2=1,fc%na -! do atom1=1,fc%na -! do k=1,3 -! do j=1,3 -! do i=1,3 -! k1=(atom1-1)*3+i -! k2=(atom2-1)*3+j -! k3=(atom3-1)*3+k -! egvprod1(i,j,k,atom1,atom2,atom3)=egv1(k1)*conjg(egv1(k2))*egv3(k3) -! egvprod2(i,j,k,atom1,atom2,atom3)=egv2(k1)*conjg(egv2(k2))*conjg(egv3(k3)) -! enddo -! enddo -! enddo -! enddo -! enddo -! enddo -! -! ! Frequency product -! omegaprod1=omega(1)*omega(1)*omega(3) -! omegaprod2=omega(2)*omega(2)*omega(3) -! omegaprod1=sqrt(omegaprod1) -! omegaprod2=sqrt(omegaprod2) -! ! The actual matrix element -! c0=0.0_r8 -! c1=0.0_r8 -! do atom1=1,fc%na -! do t=1,fc%atom(atom1)%n -! atom2=fc%atom(atom1)%triplet(t)%i2 -! atom3=fc%atom(atom1)%triplet(t)%i3 -! rv2=fc%atom(atom1)%triplet(t)%lv2 -! rv3=fc%atom(atom1)%triplet(t)%lv3 -! ! -! iqr=dot_product(-q1,rv2) -! expiqr=cmplx(cos(iqr),sin(iqr),r8) -! c0=c0+sum(fc%atom(atom1)%triplet(t)%mwm*egvprod1(:,:,:,atom1,atom2,atom3))*expiqr -! ! -! iqr=dot_product(-q2,rv2) -! expiqr=cmplx(cos(iqr),sin(iqr),r8) -! c1=c1+sum(fc%atom(atom1)%triplet(t)%mwm*egvprod2(:,:,:,atom1,atom2,atom3))*expiqr -! enddo -! enddo -! ! I predid the multiplication -! c0=enhet*c0/omegaprod1 -! c1=enhet*c1/omegaprod2 -! doublepsi=c0*c1 -! end subroutine -! end subroutine - -end module diff --git a/src/anharmonic_free_energy/energy_aux.f90 b/src/anharmonic_free_energy/energy_aux.f90 deleted file mode 100644 index 8cfc2ae7..00000000 --- a/src/anharmonic_free_energy/energy_aux.f90 +++ /dev/null @@ -1,553 +0,0 @@ - -! !> Get the spectral anharmonic free energy -! subroutine spectral_free_energy(qp,dr,uc,F3,F4,npts,unitfactor,mw) -! !> qpoint mesh -! class(lo_qpoint_mesh), intent(inout) :: qp -! !> phonon dispersions -! type(lo_phonon_dispersions), intent(in) :: dr -! !> crystal structure -! type(lo_crystalstructure), intent(in) :: uc -! !> anharmonic free energy -! real(r8), dimension(:,:), intent(in) :: F3,F4 -! !> number of points on the x-axis -! integer, intent(in) :: npts -! !> output units -! real(r8), intent(in) :: unitfactor -! !> MPI helper -! type(lo_mpi_helper), intent(in) :: mw -! -! ! -! complex(r8), dimension(3) :: v0 -! real(r8), dimension(:,:,:), allocatable :: tetvals,tetF3,tetF4,buf3,buf4,buf3b,buf4b,tetsiteproj -! real(r8), dimension(:,:), allocatable :: yp3,yp4 -! real(r8), dimension(:), allocatable :: x,yt3,yt4 -! real(r8), dimension(4) :: tete,tv3,tv4,w1,w2 -! real(r8), dimension(9) :: kernel -! real(r8), dimension(uc%na) :: tetpr -! real(r8) :: invf,sigma,deltae,t0,ftot3,ftot4,f0,f1,f2,nf3,nf4 -! integer :: q,t,i,j,k,l,ii,jj,li,u -! character(len=1000) :: opf -! -! ! Distribute q-points and tetrahedrons over MPI -! t0=walltime() -! !if ( qp%mpi%initialized .eqv. .false. ) call qp%divide_across_mpi(mw%comm) -! ! Prefetch things for tetrahedrons. -! lo_allocate(tetsiteproj(uc%na,dr%n_mode,qp%mpi%ntet)) -! lo_allocate(tetvals(4,dr%n_mode,qp%mpi%ntet)) -! lo_allocate(tetF3(4,dr%n_mode,qp%mpi%ntet)) -! lo_allocate(tetF4(4,dr%n_mode,qp%mpi%ntet)) -! tetvals=0.0_r8 -! tetsiteproj=0.0_r8 -! tetF3=0.0_r8 -! tetF4=0.0_r8 -! do li=1,qp%mpi%ntet -! i=qp%mpi%tet(li) -! do j=1,4 -! ! energies -! l=qp%tet(i)%irrind(j) -! do k=1,dr%n_mode -! tetvals(j,k,li)=dr%iq(l)%omega(k) -! tetF3(j,k,li)=F3(k,l) -! tetF4(j,k,li)=F4(k,l) -! enddo -! ! projections -! do ii=1,uc%na -! do jj=1,dr%n_mode -! v0=dr%iq(l)%egv((ii-1)*3+1:ii*3,jj) -! tetsiteproj(ii,jj,li)=tetsiteproj(ii,jj,li)+abs(dot_product(v0,v0))*0.25_r8 -! enddo -! enddo -! enddo -! enddo -! -! ! Calculate it by energy, mode, site. Make some space -! lo_allocate(buf3(uc%na,npts,dr%n_mode)) -! lo_allocate(buf4(uc%na,npts,dr%n_mode)) -! buf3=0.0_r8 -! buf4=0.0_r8 -! ! Get the x-axis -! lo_allocate(x(npts)) -! call lo_linspace(0.0_r8,dr%omega_max*1.1_r8,x) -! invf=npts/x(npts) -! sigma=dr%default_smearing() -! deltae=(x(2)-x(1))*0.25_r8 -! -! ! Now do the actual integration -! if ( mw%talk ) call lo_progressbar_init() -! do li=1,qp%mpi%ntet -! i=qp%mpi%tet(li) -! do k=1,dr%n_mode -! ! prefetch some stuff -! tete=tetvals(:,k,li) -! tv3=tetF3(:,k,li) -! tv4=tetF4(:,k,li) -! tetpr=tetsiteproj(:,k,li) -! ii=max(floor( (minval(tete)-2*deltae)*invf ),1) -! jj=min(ceiling( (maxval(tete)+2*deltae)*invf ),npts) -! ! Add it up -! do l=ii,jj -! call lo_integration_weights_for_one_tetrahedron(qp%tet(i),tete,x(l)-deltae,w1,sigma,blochlcorrections=.false.) -! call lo_integration_weights_for_one_tetrahedron(qp%tet(i),tete,x(l)+deltae,w2,sigma,blochlcorrections=.false.) -! buf3(:,l,k)=buf3(:,l,k)+tetpr*(sum( (w1+w2)*tv3 ))*0.5_r8 -! buf4(:,l,k)=buf4(:,l,k)+tetpr*(sum( (w1+w2)*tv4 ))*0.5_r8 -! enddo -! enddo -! if ( mw%talk ) then -! if ( lo_trueNtimes(li,60,qp%mpi%ntet) ) call lo_progressbar(' ... spectral free energy',li,qp%mpi%ntet) -! endif -! enddo -! ! Sum it ip -! lo_allocate(buf3b(uc%na,npts,dr%n_mode)) -! lo_allocate(buf4b(uc%na,npts,dr%n_mode)) -! buf3b=0.0_r8 -! buf4b=0.0_r8 -! call mpi_allreduce(buf3,buf3b,uc%na*dr%n_mode*npts,MPI_DOUBLE_PRECISION,MPI_SUM,mw%comm,mw%error) -! call mpi_allreduce(buf4,buf4b,uc%na*dr%n_mode*npts,MPI_DOUBLE_PRECISION,MPI_SUM,mw%comm,mw%error) -! -! if ( mw%talk ) then -! call lo_progressbar(' ... spectral free energy',li,qp%mpi%ntet,walltime()-t0) -! endif -! -! ! Scale to reasonable units -! x=x*unitfactor -! buf3b=buf3b/unitfactor -! buf4b=buf4b/unitfactor -! ! Normalize things properly. First calculate the total contribution. -! ftot3=0.0_r8 -! ftot4=0.0_r8 -! l=0 -! do i=1,qp%n_irr_point -! do j=1,dr%n_mode -! l=l+1 -! ftot3=ftot3+qp%ip(i)%weight*F3(j,i) -! ftot4=ftot4+F4(j,i)*qp%ip(i)%weight/uc%na -! enddo -! enddo -! ! Sum up the spectral to a total. -! lo_allocate(yt3(npts)) -! lo_allocate(yt4(npts)) -! yt3=0.0_r8 -! yt4=0.0_r8 -! do j=1,dr%n_mode -! do i=1,uc%na -! yt3=yt3+buf3b(i,:,j) -! yt4=yt4+buf4b(i,:,j) -! enddo -! enddo -! nf3=ftot3/lo_trapezoid_integration(x,yt3) -! nf4=ftot4/lo_trapezoid_integration(x,yt4) -! yt3=yt3*nf3 -! yt4=yt4*nf4 -! ! Now construct the site-projected -! lo_allocate(yp3(npts,uc%na)) -! lo_allocate(yp4(npts,uc%na)) -! yp3=0.0_r8 -! yp4=0.0_r8 -! do j=1,dr%n_mode -! do i=1,uc%na -! yp3(:,i)=yp3(:,i)+buf3b(i,:,j) -! yp4(:,i)=yp4(:,i)+buf4b(i,:,j) -! enddo -! enddo -! ! Make sure the site-projected add up to the total -! do i=1,npts -! f0=abs(sum(yp3(i,:))) -! if ( f0 .gt. 1E-30_r8 ) then -! yp3(i,:)=yp3(i,:)*abs(yt3(i))/f0 -! else -! yp3(i,:)=0.0_r8 -! endif -! f0=abs(sum(yp4(i,:))) -! if ( f0 .gt. 1E-30_r8 ) then -! yp4(i,:)=yp4(i,:)*yt4(i)/f0 -! else -! yp4(i,:)=0.0_r8 -! endif -! enddo -! -! ! Dump to file -! if ( mw%talk ) then -! ! output format -! u=open_file('out','dumspf') -! opf="("//tochar(uc%na*2+3)//"(2X,E18.12))" -! do i=1,npts -! write(u,opf) x(i),yt3(i),yt4(i),yp3(i,:),yp4(i,:) -! enddo -! close(u) -! endif -! -! end subroutine - -! !> Calculate all scattering rates, MPI-distributed -! subroutine getscatteringrates(sr,qpoint,ompoint,qp,dr,uc,fc,fct,fcf,verbosity,mw) -! !> scattering rates -! class(lo_listofscatteringrates), intent(out) :: sr -! !> q-point in question -! type(lo_qpoint) :: qpoint -! !> harmonic properties -! type(lo_phonon_dispersions_qpoint), intent(in) :: ompoint -! !> qpoint mesh -! class(lo_qpoint_mesh), intent(in) :: qp -! !> phonon dispersions -! type(lo_phonon_dispersions), intent(in) :: dr -! !> crystal structure -! type(lo_crystalstructure), intent(in) :: uc -! !> second order forceconstant -! type(lo_forceconstant_secondorder), intent(inout) :: fc -! !> third order force constant -! type(lo_forceconstant_thirdorder), intent(in) :: fct -! !> fourth order force constants -! type(lo_forceconstant_fourthorder), intent(in) :: fcf -! !> how much to talk -! integer, intent(in) :: verbosity -! !> MPI communicator -! type(lo_mpi_helper), intent(in) :: mw -! -! ! Just keep a list of q3, temporarily -! type(lo_qpoint) :: qpgamma -! type(lo_phonon_dispersions_qpoint) :: ompgamma -! real(r8), dimension(:,:), allocatable :: qvec3 -! complex(r8), dimension(:,:,:), allocatable :: egv3 -! -! ! First get the third frequency at all q-points -! thirdfreq: block -! type(lo_qpoint) :: dq3 -! type(lo_phonon_dispersions_qpoint) :: ompoint -! complex(r8), dimension(:,:,:), allocatable :: egv3buf -! complex(r8), dimension(:,:,:), allocatable :: Dq -! complex(r8), dimension(:,:), allocatable :: D -! real(r8), dimension(:,:), allocatable :: om3buf,qv3buf -! real(r8), dimension(:,:,:), allocatable :: vel3buf -! real(r8), dimension(3) :: qv1,qv2,qv3 -! real(r8) :: t0 -! integer :: lq,q,b1,b2,l -! -! ! Gamma-point things -! qpgamma%r=0.0_r8 -! qpgamma%r=0.0_r8 -! call lo_get_small_group_of_qpoint(qpgamma,uc) -! lo_allocate(ompgamma%omega(dr%n_mode)) -! lo_allocate(ompgamma%vel(3,dr%n_mode)) -! lo_allocate(ompgamma%egv(dr%n_mode,dr%n_mode)) -! lo_allocate(ompgamma%degeneracy(dr%n_mode)) -! lo_allocate(ompgamma%degenmode(dr%n_mode,dr%n_mode)) -! write(*,*) 'fixme generate thingy' -! !call ompgamma%generate(fc,uc,qpgamma) -! -! lo_allocate(sr%omega_gamma(dr%n_mode)) -! sr%omega_gamma=ompgamma%omega -! -! t0=walltime() -! lo_allocate(om3buf(dr%n_mode,qp%n_full_point)) -! lo_allocate(vel3buf(3,dr%n_mode,qp%n_full_point)) -! lo_allocate(egv3buf(dr%n_mode,dr%n_mode,qp%n_full_point)) -! lo_allocate(qv3buf(3,qp%n_full_point)) -! qv3buf=0.0_r8 -! om3buf=0.0_r8 -! vel3buf=0.0_r8 -! egv3buf=0.0_r8 -! lo_allocate(Dq(dr%n_mode,dr%n_mode,3)) -! lo_allocate(D(dr%n_mode,dr%n_mode)) -! ! Calculate all the frequencies and stuff for the third q-point -! write(*,*) 'FIXME MPI' -! ! do lq=1,qp%mpi%nqtot -! ! q=qp%mpi%qtot(lq) -! ! -! ! ! Get the q-vectors -! ! qv1=qpoint%r -! ! qv2=qp%ap(q)%r -! ! qv3=-qv1-qv2 -! ! ! Frequencies and stuff at the third point -! ! dq3%r=qv3 -! ! dq3%r=dq3%r-uc%bz%gshift(dq3%r) -! ! ! store third q-point for later -! ! qv3buf(:,q)=dq3%r -! ! ! get phonon frequencies -! ! call lo_get_small_group_of_qpoint(dq3,uc) -! ! call fc%dynamicalmatrix(uc,dq3,D,Dq) -! ! call fc%frequencies_eigenvectors_groupvelocities(uc,D,Dq,om3buf(:,q),egv3buf(:,:,q),vel3buf(:,:,q),dq3) -! ! enddo -! ! Communicate this to all ranks -! lo_allocate(sr%omega3(dr%n_mode,qp%n_full_point)) -! lo_allocate(sr%vel3(3,dr%n_mode,qp%n_full_point)) -! lo_allocate(egv3(dr%n_mode,dr%n_mode,qp%n_full_point)) -! lo_allocate(qvec3(3,qp%n_full_point)) -! sr%omega3=0.0_r8 -! sr%vel3=0.0_r8 -! egv3=0.0_r8 -! qvec3=0.0_r8 -! call mpi_allreduce(om3buf,sr%omega3,dr%n_mode*qp%n_full_point,MPI_DOUBLE_PRECISION,MPI_SUM,mw%comm,mw%error) -! call mpi_allreduce(vel3buf,sr%vel3,3*dr%n_mode*qp%n_full_point,MPI_DOUBLE_PRECISION,MPI_SUM,mw%comm,mw%error) -! call mpi_allreduce(egv3buf,egv3,dr%n_mode*dr%n_mode*qp%n_full_point,MPI_DOUBLE_COMPLEX,MPI_SUM,mw%comm,mw%error) -! call mpi_allreduce(qv3buf,qvec3,3*qp%n_full_point,MPI_DOUBLE_PRECISION,MPI_SUM,mw%comm,mw%error) -! if ( verbosity .gt. 0 ) then -! write(*,*) '' -! write(*,*) "... got q'' frequencies in ",tochar(walltime()-t0),'s' -! endif -! ! cleanup -! lo_deallocate(om3buf) -! lo_deallocate(vel3buf) -! lo_deallocate(egv3buf) -! lo_deallocate(qv3buf) -! lo_deallocate(Dq) -! lo_deallocate(D) -! end block thirdfreq -! -! !> get the threephonon matrix elements -! threephsc: block -! complex(r8), dimension(:,:), allocatable :: egv -! complex(r8) :: c0 -! real(r8), dimension(:,:,:,:), allocatable :: psibuf,dblbuf -! real(r8), dimension(3) :: qv1,qv2,qv3,omega -! real(r8) :: t0,f0 -! integer :: q,b1,b2,b3,l,k,ii,jj,kk,bb1,bb2,bb3,n1,n2,n3 -! logical, dimension(:,:,:), allocatable :: fixdeg -! -! lo_allocate(psibuf(dr%n_mode,dr%n_mode,dr%n_mode,qp%n_full_point)) -! lo_allocate(dblbuf(dr%n_mode,dr%n_mode,dr%n_mode,qp%n_full_point)) -! lo_allocate(egv(dr%n_mode,3)) -! psibuf=0.0_r8 -! dblbuf=0.0_r8 -! egv=0.0_r8 -! -! t0=walltime() -! if ( verbosity .gt. 0 ) call lo_progressbar_init() -! l=0 -! k=0 -! -! do q=1,qp%n_full_point -! qv1=-qpoint%r*lo_twopi -! qv2=-qp%ap(q)%r*lo_twopi -! qv3=-qvec3(:,q)*lo_twopi -! do b1=1,dr%n_mode -! do b2=1,dr%n_mode -! do b3=1,dr%n_mode -! ! MPI division -! l=l+1 -! if ( mod(l,mw%n) .ne. mw%r ) cycle -! omega(1)=ompoint%omega(b1) -! omega(2)=dr%aq(q)%omega(b2) -! omega(3)=sr%omega3(b3,q) -! ! prefetch eigenvectors -! egv(:,1)=ompoint%egv(:,b1) -! egv(:,2)=dr%aq(q)%egv(:,b2) -! egv(:,3)=egv3(:,b3,q) -! ! To finally get the scattering rates -! if ( minval(omega) .gt. dr%omega_min*0.5_r8 ) then -! c0=fct%scatteringamplitude(omega,egv,qv2,qv3) -! psibuf(b1,b2,b3,q)=abs(conjg(c0)*c0) -! else -! psibuf(b1,b2,b3,q)=0.0_r8 -! endif -! ! And perhaps the double scattering rate thingy -! if ( ompgamma%omega(b3) .gt. dr%omega_min*0.5_r8 ) then -! ! b3 needs to be an optical mode -! omega(3)=ompgamma%omega(b3) -! egv(:,3)=ompgamma%egv(:,b3) -! ! And the weird double scatteringrates -! dblbuf(b1,b2,b3,q)=0.0_r8 !real(double_scatteringamplitude(fct,omega,egv,qv1,qv2)) -! else -! dblbuf(b1,b2,b3,q)=0.0_r8 -! endif -! enddo -! enddo -! if ( verbosity .gt. 0 ) then -! k=k+1 -! if ( lo_trueNtimes(k,127,qp%n_full_point*dr%n_mode) ) call lo_progressbar(' ... threephonon matrixelements',k,qp%n_full_point*dr%n_mode) -! endif -! enddo -! enddo -! lo_allocate(sr%psi_3ph_sq(dr%n_mode,dr%n_mode,dr%n_mode,qp%n_full_point)) -! lo_allocate(sr%psi_3ph_db(dr%n_mode,dr%n_mode,dr%n_mode,qp%n_full_point)) -! sr%psi_3ph_sq=0.0_r8 -! sr%psi_3ph_db=0.0_r8 -! ! sum it up -! call mpi_allreduce(psibuf,sr%psi_3ph_sq,dr%n_mode*dr%n_mode*dr%n_mode*qp%n_full_point,MPI_DOUBLE_PRECISION,MPI_SUM,mw%comm,mw%error) -! call mpi_allreduce(dblbuf,sr%psi_3ph_db,dr%n_mode*dr%n_mode*dr%n_mode*qp%n_full_point,MPI_DOUBLE_PRECISION,MPI_SUM,mw%comm,mw%error) -! if ( verbosity .gt. 0 ) call lo_progressbar(' ... threephonon matrixelements',qp%n_full_point*dr%n_mode,qp%n_full_point*dr%n_mode,walltime()-t0) -! end block threephsc -! -! ! And the four-phonon scattering elements -! fourphsc: block -! complex(r8), dimension(:,:), allocatable :: dumegv1,dumegv2,dumegv3,dumegv4,egv -! complex(r8) :: c0 -! real(r8), dimension(:,:,:), allocatable :: psibuf -! real(r8), dimension(:), allocatable :: dumom1,dumom2,dumom3,dumom4 -! real(r8), dimension(4) :: omega -! real(r8), dimension(3) :: qv1,qv2,qv3,qv4 -! real(r8) :: omegathres,t0 -! integer :: b1,b2,b3,b4,q1,ctr -! -! t0=walltime() -! lo_allocate(psibuf(dr%n_mode,dr%n_mode,qp%n_full_point)) -! psibuf=0.0_r8 -! ! For the other q-points -! lo_allocate(dumom1(dr%n_mode)) -! lo_allocate(dumom2(dr%n_mode)) -! lo_allocate(dumom3(dr%n_mode)) -! lo_allocate(dumom4(dr%n_mode)) -! lo_allocate(dumegv1(dr%n_mode,dr%n_mode)) -! lo_allocate(dumegv2(dr%n_mode,dr%n_mode)) -! lo_allocate(dumegv3(dr%n_mode,dr%n_mode)) -! lo_allocate(dumegv4(dr%n_mode,dr%n_mode)) -! lo_allocate(egv(dr%n_mode,4)) -! dumom1=0.0_r8 -! dumom2=0.0_r8 -! dumom3=0.0_r8 -! dumom4=0.0_r8 -! dumegv1=0.0_r8 -! dumegv2=0.0_r8 -! dumegv3=0.0_r8 -! dumegv4=0.0_r8 -! omegathres=dr%omega_min*0.5_r8 -! ctr=0 -! if ( verbosity .gt. 0 ) call lo_progressbar_init() -! do q1=1,qp%n_full_point -! dumom1=ompoint%omega -! dumom2=ompoint%omega -! dumom3=dr%aq(q1)%omega -! dumom4=dr%aq(q1)%omega -! dumegv1=ompoint%egv -! dumegv2=conjg(ompoint%egv) -! dumegv3=dr%aq(q1)%egv -! dumegv4=conjg(dr%aq(q1)%egv) -! qv1=qpoint%r*lo_twopi -! qv2=-qpoint%r*lo_twopi -! qv3=qp%ap(q1)%r*lo_twopi -! qv4=-qp%ap(q1)%r*lo_twopi -! do b1=1,dr%n_mode -! b2=b1 -! ! mpit thingy -! ctr=ctr+1 -! if ( mod(ctr,mw%n) .ne. mw%r ) cycle -! do b3=1,dr%n_mode -! b4=b3 -! omega=[dumom1(b1),dumom2(b2),dumom3(b3),dumom4(b4)] -! egv(:,1)=dumegv1(:,b1) -! egv(:,2)=dumegv2(:,b2) -! egv(:,3)=dumegv3(:,b3) -! egv(:,4)=dumegv4(:,b4) -! if ( minval(omega) .gt. omegathres ) then -! c0=fcf%scatteringamplitude(omega,egv,qv2,qv3,qv4) -! else -! c0=0.0_r8 -! endif -! psibuf(b1,b3,q1)=real(c0) -! enddo -! ! -! if ( verbosity .gt. 0 ) then -! if ( lo_trueNtimes(ctr,127,qp%n_full_point*dr%n_mode) ) call lo_progressbar(' ... fourphonon matrixelements',ctr,qp%n_full_point*dr%n_mode) -! endif -! enddo -! enddo -! lo_allocate(sr%psi_4ph(dr%n_mode,dr%n_mode,qp%n_full_point)) -! sr%psi_4ph=0.0_r8 -! call mpi_allreduce(psibuf,sr%psi_4ph,dr%n_mode*dr%n_mode*qp%n_full_point,MPI_DOUBLE_PRECISION,MPI_SUM,mw%comm,mw%error) -! if ( verbosity .gt. 0 ) call lo_progressbar(' ... fourphonon matrixelements',qp%n_full_point*dr%n_mode,qp%n_full_point*dr%n_mode,walltime()-t0) -! end block fourphsc -! -! end subroutine - -! !> harmonic properties at specific q-vector -! subroutine harmonic_things_at_single_q(q,uc,fc,loto,ompoint) -! !> Cartesian coordinates of the q-point in question -! real(r8), dimension(3), intent(in) :: q -! !> crystal structure -! type(lo_crystalstructure), intent(in) :: uc -! !> second order force constant -! type(lo_forceconstant_secondorder), intent(in) :: fc -! !> electrostatic corrections -! type(lo_loto), intent(in) :: loto -! !> harmonic properties at this q-point -! type(lo_phonon_dispersions_qpoint), intent(out) :: ompoint -! -! type(lo_qpoint) :: qpoint -! complex(r8), dimension(:,:,:), allocatable :: Dq -! complex(r8), dimension(:,:), allocatable :: D -! integer :: nb -! ! -! nb=uc%na*3 -! qpoint%v=q -! qpoint%w=qpoint%v-uc%bz%gshift(q+lo_degenvector) -! call lo_get_small_group_of_qpoint(qpoint,uc) -! lo_allocate(ompoint%omega(nb)) -! lo_allocate(ompoint%vel(3,nb)) -! lo_allocate(ompoint%egv(nb,nb)) -! lo_allocate(D(nb,nb)) -! lo_allocate(Dq(3,nb,nb)) -! call lo_get_dynamical_matrix(fc,uc,qpoint,loto,D,Dq) -! call lo_get_omega_and_velocities(D,Dq,uc,ompoint%omega,ompoint%egv,ompoint%vel,qpoint=qpoint) -! lo_deallocate(D) -! lo_deallocate(Dq) -! end subroutine - -! !> The three-phonon matrix element, but product of two complex thingies -! pure complex(r8) function double_scatteringamplitude(fc,omega,egv,q1,q2) -! !> the third order force constant -! class(lo_forceconstant_thirdorder), intent(in) :: fc -! !> the frequencies in question -! real(r8), dimension(3), intent(in) :: omega -! !> the eigenvectors -! complex(r8), dimension(:,:), intent(in) :: egv -! !> the two q-vectors that matter -! real(r8), dimension(3), intent(in) :: q1,q2 -! ! -! integer :: atom1,atom2,atom3,i,j,k,k1,k2,k3,t -! complex(r8) :: expiqr,c0,c1 -! real(r8), dimension(3) :: rv2,rv3 -! real(r8) :: iqr,omegaprod1,omegaprod2,enhet -! ! -! complex(r8), dimension(:,:,:,:,:,:), allocatable :: egvprod1,egvprod2 -! ! -! ! Not enough room on the stack for large unitcells, have to allocate space -! allocate(egvprod1(3,3,3,fc%na,fc%na,fc%na)) -! allocate(egvprod2(3,3,3,fc%na,fc%na,fc%na)) -! ! Eigenvector product -! do atom3=1,fc%na -! do atom2=1,fc%na -! do atom1=1,fc%na -! do k=1,3 -! do j=1,3 -! do i=1,3 -! k1=(atom1-1)*3+i -! k2=(atom2-1)*3+j -! k3=(atom3-1)*3+k -! egvprod1(i,j,k,atom1,atom2,atom3)=egv(k1,1)*conjg(egv(k2,1))*egv(k3,3) -! egvprod2(i,j,k,atom1,atom2,atom3)=egv(k1,2)*conjg(egv(k2,2))*conjg(egv(k3,3)) -! enddo -! enddo -! enddo -! enddo -! enddo -! enddo -! ! Frequency product -! omegaprod1=omega(1)*omega(1)*omega(3) -! omegaprod2=omega(2)*omega(2)*omega(3) -! omegaprod1=sqrt(omegaprod1) -! omegaprod2=sqrt(omegaprod2) -! ! The actual matrix element -! c0=0.0_r8 -! c1=0.0_r8 -! do atom1=1,fc%na -! do t=1,fc%atom(atom1)%n -! atom2=fc%atom(atom1)%triplet(t)%i2 -! atom3=fc%atom(atom1)%triplet(t)%i3 -! rv2=fc%atom(atom1)%triplet(t)%lv2 -! rv3=fc%atom(atom1)%triplet(t)%lv3 -! ! -! iqr=dot_product(-q1,rv2) !+dot_product(q3,rv3) -! expiqr=cmplx(cos(iqr),sin(iqr),r8) -! c0=c0+sum(fc%atom(atom1)%triplet(t)%mwm*egvprod1(:,:,:,atom1,atom2,atom3))*expiqr -! ! -! iqr=dot_product(-q2,rv2) !+dot_product(-q3,rv3) -! expiqr=cmplx(cos(iqr),sin(iqr),r8) -! c1=c1+sum(fc%atom(atom1)%triplet(t)%mwm*egvprod2(:,:,:,atom1,atom2,atom3))*expiqr -! enddo -! enddo -! ! I predid the multiplication -! enhet=2.367755374064161E51_r8 -! c0=enhet*c0/omegaprod1 -! c1=enhet*c1/omegaprod2 -! ! -! double_scatteringamplitude=c0*c1 -! end function diff --git a/src/anharmonic_free_energy/energy_dos.f90 b/src/anharmonic_free_energy/energy_dos.f90 deleted file mode 100644 index 34f5e538..00000000 --- a/src/anharmonic_free_energy/energy_dos.f90 +++ /dev/null @@ -1,173 +0,0 @@ - -!!> calculate things as a density of states -!subroutine get_free_energy_on_grid(qpd,drd,uc,fc,fct,fcf,qp,dr,loto,opts,mw,lsmpi) -! !> q-point mesh -! type(lo_monkhorst_pack_mesh), intent(in) :: qpd -! !> harmonic properties on this mesh -! type(lo_phonon_dispersions), intent(in) :: drd -! !> crystal structure -! type(lo_crystalstructure), intent(inout) :: uc -! !> second order force constant -! type(lo_forceconstant_secondorder), intent(in) :: fc -! !> third order force constant -! type(lo_forceconstant_thirdorder), intent(in) :: fct -! !> fourth order force constant -! type(lo_forceconstant_fourthorder), intent(in) :: fcf -! !> q-point mesh -! type(lo_monkhorst_pack_mesh), intent(in) :: qp -! !> harmonic properties on this mesh -! type(lo_phonon_dispersions), intent(in) :: dr -! !> electrostatic corrections -! type(lo_loto), intent(in) :: loto -! !> all settings -! type(lo_opts), intent(in) :: opts -! !> mpi communicator -! type(lo_mpiinfo), intent(in) :: mw -! !> mpi helper -! type(lo_lsmpi), intent(in) :: lsmpi -! -! ! stuff for the DOS mesh -! type(lo_phonon_selfenergy) :: se -! type(lo_phonon_dos) :: pd -! complex(flyt), dimension(3) :: cv0 -! real(flyt), dimension(:,:,:), allocatable :: dumdos,dumdosbuf -! real(flyt), dimension(:,:), allocatable :: dum_site,dum_mode -! real(flyt), dimension(:), allocatable :: dum -! real(flyt) :: f0,f1,t0,sigma,weight -! integer :: q1,lqp,mode,i -! -! t0=mpi_wtime() -! ! switch off openMP -! call omp_set_num_threads(1) -! -! if ( mw%talk ) call lo_progressbar_init() -! lo_allocate(dumdos(opts%nf,dr%nb,qpd%nq_irr)) -! lo_allocate(dumdosbuf(opts%nf,dr%nb,qpd%nq_irr)) -! dumdos=0.0_flyt -! dumdosbuf=0.0_flyt -! do q1=1,lsmpi%nq -! lqp=lsmpi%ind(q1) -! ! get the actual self-energy -! call se%generate(qpd%ip(lqp),drd%iq(lqp),uc,fc,fct,fcf,qp,dr,loto,opts) -! ! and the intensity -! do mode=1,drd%nb -! call getintensity(se%faxis,se%im_3ph(:,mode)+se%im_iso(:,mode),& -! se%re_3ph(:,mode)+se%re_4ph(:,mode),se%p%omega(mode),se%faxis,& -! se%intensity(:,mode)) -! f0=lo_trapezoid_integration(se%faxis,se%intensity(:,mode)) -! ! if it's tiny, add a really narry gaussian instead. -! if ( f0 .lt. lo_tol ) then -! if ( drd%iq(q1)%omega(mode) .gt. drd%omega_min*0.5_flyt ) then -! do i=1,se%nf -! se%intensity(i,mode)=lo_gauss(se%faxis(i),drd%iq(lqp)%omega(mode),abs(se%faxis(3)-se%faxis(1))) -! enddo -! endif -! endif -! ! store the intensities -! dumdosbuf(:,mode,lqp)=dumdosbuf(:,mode,lqp)+se%intensity(:,mode) -! enddo -! ! -! if ( mw%talk ) call lo_progressbar(' ... calculating phonon dos',q1,lsmpi%nq,mpi_wtime()-t0) -! ! -! enddo -! -! ! Sum it up -! call mpi_allreduce(dumdosbuf,dumdos,qpd%nq_irr*opts%nf*dr%nb,MPI_DOUBLE_PRECISION,MPI_SUM,mw%comm,mw%error) -! -! ! Build the phonon dos structure -! lo_allocate(pd%omega(opts%nf)) -! lo_allocate(pd%pdos_site(opts%nf,uc%na)) -! lo_allocate(pd%pdos_mode(opts%nf,dr%nb)) -! lo_allocate(pd%dos(opts%nf)) -! pd%na=uc%na -! pd%nb=dr%nb -! pd%ndos=opts%nf -! pd%enhet=opts%enhet -! pd%omega=se%intensityaxis -! pd%pdos_site=0.0_flyt -! pd%pdos_mode=0.0_flyt -! pd%dos=0.0_flyt -! pd%dosprojection=.true. -! pd%dossmear=drd%default_smearing() -! pd%dosmax=maxval(pd%omega) -! -! t0=mpi_wtime() -! ! Add it up, with a little smearing -! lo_allocate(dum_site(pd%ndos,pd%na)) -! lo_allocate(dum_mode(pd%ndos,pd%nb)) -! lo_allocate(dum(pd%ndos)) -! dum_site=0.0_flyt -! dum_mode=0.0_flyt -! if ( mw%talk ) call lo_progressbar_init() -! do q1=1,lsmpi%nq -! lqp=lsmpi%ind(q1) -! weight=qpd%ip(lqp)%weight -! ! -! do mode=1,drd%nb -! ! skip acoustic at gamma -! if ( drd%iq(q1)%omega(mode) .lt. drd%omega_min*0.5_flyt ) cycle -! ! ok, smear a little -! sigma=qpd%smearingparameter(drd%iq(lqp)%vel(:,mode),pd%dossmear,opts%sigma) -! call lo_put_function_on_new_axis(se%faxis,dumdos(:,mode,lqp),pd%omega,dum,sigma) -! ! make sure it's normalized after convolution -! dum=dum/lo_trapezoid_integration(pd%omega,dum) -! dum=dum*weight -! ! add it to the mode-projected -! dum_mode(:,mode)=dum_mode(:,mode)+dum -! ! get the site-projection thing -! do i=1,uc%na -! cv0=drd%iq(lqp)%egv((i-1)*3+1:i*3,mode) -! f0=abs(dot_product(cv0,conjg(cv0))) -! dum_site(:,i)=dum_site(:,i)+f0*dum -! enddo -! enddo -! ! -! if ( mw%talk ) call lo_progressbar(' ... integrating phonon dos',q1,lsmpi%nq,mpi_wtime()-t0) -! ! -! enddo -! -! ! Add things together -! call mpi_allreduce(dum_site,pd%pdos_site,opts%nf*uc%na,MPI_DOUBLE_PRECISION,MPI_SUM,mw%comm,mw%error) -! call mpi_allreduce(dum_mode,pd%pdos_mode,opts%nf*dr%nb,MPI_DOUBLE_PRECISION,MPI_SUM,mw%comm,mw%error) -! -! if ( mw%r .eq. 0 ) then -! ! Start normalizing, first the whole thing -! do mode=1,drd%nb -! pd%dos=pd%dos+pd%pdos_mode(:,mode) -! f0=lo_trapezoid_integration(pd%omega,pd%pdos_mode(:,mode)) -! pd%pdos_mode=pd%pdos_mode/f0 -! enddo -! ! remove stupid stuff -! f1=pd%dos(1) -! do i=1,pd%ndos -! f0=(pd%ndos-i)*1.0_flyt/( (pd%ndos-1)*1.0_flyt ) -! f0=f0**2 -! pd%dos(i)=pd%dos(i)-f0*f1 -! if ( pd%dos(i) .lt. 0.0_flyt ) pd%dos(i)=0.0_flyt -! enddo -! pd%dos(1)=0.0_flyt -! ! -! f0=lo_trapezoid_integration(pd%omega,pd%dos) -! pd%dos=pd%dos*dr%nb/f0 -! ! and the site-projected -! do i=1,uc%na -! f0=lo_trapezoid_integration(pd%omega,pd%pdos_site(:,i)) -! pd%pdos_site(:,i)=pd%pdos_site(:,i)/f0 -! enddo -! ! make sure the pojected adds up to the total -! do i=1,pd%ndos -! if ( pd%dos(i) .gt. lo_tol/lo_twopi/1E12_flyt ) then -! f0=sum(pd%pdos_mode(i,:)) -! pd%pdos_mode(i,:)=pd%pdos_mode(i,:)*pd%dos(i)/f0 -! f0=sum(pd%pdos_site(i,:)) -! pd%pdos_site(i,:)=pd%pdos_site(i,:)*pd%dos(i)/f0 -! endif -! enddo -! ! Write it to file -! call pd%write_to_file(uc,opts%enhet,pdfplot=.false.,modeproj=.false.,& -! filename='outfile.phonon_dos_lineshape') -! ! -! endif -! -!end subroutine - diff --git a/src/anharmonic_free_energy/epot.f90 b/src/anharmonic_free_energy/epot.f90 index 9085ea65..6fe171c7 100644 --- a/src/anharmonic_free_energy/epot.f90 +++ b/src/anharmonic_free_energy/epot.f90 @@ -1,168 +1,71 @@ module epot !! Deal with many kinds of potential energy differences -use konstanter, only: r8, lo_pi, lo_twopi, lo_tol, lo_sqtol, lo_status, lo_Hartree_to_eV, lo_kb_hartree -use gottochblandat, only: tochar, walltime, lo_chop, lo_trueNtimes, lo_progressbar_init, & - lo_progressbar, lo_frobnorm, open_file, lo_flattentensor, lo_sqnorm, lo_outerproduct, lo_mean, & - lo_points_on_sphere, lo_mean, lo_stddev +use konstanter, only: r8, lo_kb_hartree +use gottochblandat, only: tochar, walltime, lo_mean, lo_stddev, & + lo_trueNtimes, lo_progressbar_init, lo_progressbar use mpi_wrappers, only: lo_mpi_helper, lo_stop_gracefully use lo_memtracker, only: lo_mem_helper -!use geometryfunctions, only: lo_inscribed_sphere_in_box use type_crystalstructure, only: lo_crystalstructure use type_forceconstant_secondorder, only: lo_forceconstant_secondorder use type_forceconstant_thirdorder, only: lo_forceconstant_thirdorder use type_forceconstant_fourthorder, only: lo_forceconstant_fourthorder use type_mdsim, only: lo_mdsim + +use konstanter, only: lo_Hartree_to_eV + +use lo_thermodynamic_helpers, only: lo_thermodynamics, lo_full_to_voigt_33, lo_voigt_to_full_33 implicit none private public :: lo_energy_differences type lo_energy_differences - ! forceconstants needed for evaluation + !> forceconstants needed for evaluation type(lo_forceconstant_secondorder) :: fc2 type(lo_forceconstant_thirdorder) :: fc3 type(lo_forceconstant_fourthorder) :: fc4 + !> Holder for long range part of the force constants real(r8), dimension(:, :, :, :), allocatable :: fcp + !> Is it a polar material ? logical :: polar = .false. contains procedure :: setup => setup_potential_energy_differences - procedure :: statistical_sampling procedure :: energies_and_forces + procedure :: compute_realspace_thermo end type contains -!> statistically sample -subroutine statistical_sampling(pot, uc, ss, fc, temperature, mw, mem, verbosity) - !> container for potential energy differences - class(lo_energy_differences), intent(inout) :: pot - !> unitcell - type(lo_crystalstructure), intent(in) :: uc - !> supercell - type(lo_crystalstructure), intent(in) :: ss - !> second order forceconstant - type(lo_forceconstant_secondorder), intent(in) :: fc - !> temperature - real(r8), intent(in) :: temperature - !> MPI helper - type(lo_mpi_helper), intent(inout) :: mw - !> memory tracker - type(lo_mem_helper), intent(inout) :: mem - !> talk a lot? - integer, intent(in) :: verbosity - - type(lo_crystalstructure) :: p - integer, parameter :: ninner = 20, nouter = 40 - integer :: initer, outiter, nstep, ctr, i - real(r8), dimension(:, :), allocatable :: ebuf, rbuf - real(r8), dimension(:, :), allocatable :: f2, f3, f4, fp - real(r8) :: e2, e3, e4, ep, deltaE, expdeltaE, ikbt, tomev, emean - - ! Copy of structure to work with - p = ss - - ! Total number of steps we are doing? - nstep = ninner*nouter - - ! Some helper space - call mem%allocate(ebuf, [nstep, 3], persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%allocate(rbuf, [3, mw%n], persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - ebuf = 0.0_r8 - rbuf = 0.0_r8 - - ! Dummy space for force - call mem%allocate(f2, [3, ss%na], persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%allocate(f3, [3, ss%na], persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%allocate(f4, [3, ss%na], persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%allocate(fp, [3, ss%na], persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - f2 = 0.0_r8 - f3 = 0.0_r8 - f4 = 0.0_r8 - fp = 0.0_r8 - - ! Thermal factor? - ikbt = 1.0_r8/(temperature*lo_kb_hartree) - tomev = lo_Hartree_to_eV*1000 - - ctr = 0 - outloop: do outiter = 1, nouter - inloop: do initer = 1, ninner - ctr = ctr + 1 - - ! Reset structure - p%u = 0.0_r8 - p%v = 0.0_r8 - p%r = ss%r - ! Get new structure - call pot%fc2%initialize_cell(p, uc, fc, temperature, .true., .false., -1.0_r8, mw, nosync=.true.) - ! Calculate the energy - call pot%energies_and_forces(p%u, e2, e3, e4, ep, f2, f3, f4, fp) - e2 = e2 !/ss%na - e3 = e3 !/ss%na - e4 = e4 !/ss%na - ep = ep !/ss%na - - ! H1-H0 difference - deltaE = e3 + e4 - expdeltaE = exp(-deltaE*ikbt) - ebuf(ctr, 1) = deltaE - ebuf(ctr, 2) = expdeltaE - end do inloop - - ! Get new mean energy - emean = lo_mean(ebuf(1:ctr, 1))/mw%n - call mw%allreduce('sum', emean) - do i = 1, ctr - ebuf(i, 3) = ebuf(i, 1) - emean - ebuf(i, 3) = exp(-ebuf(i, 3)*ikbt) - end do - - ! Print a little summary - rbuf = 0.0_r8 - rbuf(1, mw%r + 1) = lo_mean(ebuf(1:ctr, 1))/ss%na - rbuf(2, mw%r + 1) = -log(lo_mean(ebuf(1:ctr, 2)))/ikbt/ss%na - rbuf(3, mw%r + 1) = -log(lo_mean(ebuf(1:ctr, 3)))/ikbt/ss%na + emean/ss%na - call mw%allreduce('sum', rbuf) - - if (verbosity .gt. 0) then - write (*, *) ctr, lo_mean(rbuf(3, :))*tomev, lo_mean(rbuf(2, :))*tomev, lo_stddev(rbuf(1, :))*tomev, lo_stddev(rbuf(2, :))*tomev - end if - end do outloop - - call mem%deallocate(ebuf, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%deallocate(rbuf, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%deallocate(f2, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%deallocate(f3, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%deallocate(f4, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) - call mem%deallocate(fp, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) -end subroutine - ! !> calculate energies and forces for a given configuration -subroutine energies_and_forces(pot, u, e2, e3, e4, ep, f2, f3, f4, fp) +subroutine energies_and_forces(pot, ss, u, e2, e3, e4, ep, s3) + !> The unitcell + type(lo_crystalstructure), intent(in) :: ss !> container for potential energy differences class(lo_energy_differences), intent(in) :: pot !> displacements real(r8), dimension(:, :), intent(in) :: u !> energies real(r8), intent(out) :: e2, e3, e4, ep - !> forces - real(r8), dimension(:, :), intent(out) :: f2, f3, f4, fp + !> stress + real(r8), dimension(3, 3), intent(out) :: s3 + !> Fourth order IFC real(r8), dimension(3, 3, 3, 3) :: m4 + !> Third order IFC real(r8), dimension(3, 3, 3) :: m3 + !> Second order IFC real(r8), dimension(3, 3) :: m2 - real(r8), dimension(3) :: v0, u2, u3, u4 - integer :: a1, a2, a3, a4, i1, i2, i3, i4, i + !> Forces and displacements + real(r8), dimension(3) :: v0, u1, u2, u3, u4 + !> Some integers + integer :: a1, a2, a3, a4, i1, i2, i3, i4, i5, i e2 = 0.0_r8 e3 = 0.0_r8 e4 = 0.0_r8 ep = 0.0_r8 - f2 = 0.0_r8 - f3 = 0.0_r8 - f4 = 0.0_r8 - fp = 0.0_r8 + s3 = 0.0_r8 ! pair term do a1 = 1, size(u, 2) @@ -173,7 +76,6 @@ subroutine energies_and_forces(pot, u, e2, e3, e4, ep, f2, f3, f4, fp) v0 = v0 - matmul(m2, u(:, a2)) end do e2 = e2 - dot_product(u(:, a1), v0)*0.5_r8 - f2(:, a1) = v0 end do ! polar term @@ -185,7 +87,6 @@ subroutine energies_and_forces(pot, u, e2, e3, e4, ep, f2, f3, f4, fp) v0 = v0 - matmul(pot%fcp(:, :, a1, a2), u(:, a2)) end do ep = ep - dot_product(u(:, a1), v0)*0.5_r8 - fp(:, a1) = v0 end do end if @@ -197,18 +98,21 @@ subroutine energies_and_forces(pot, u, e2, e3, e4, ep, f2, f3, f4, fp) m3 = pot%fc3%atom(a1)%triplet(i)%m a2 = pot%fc3%atom(a1)%triplet(i)%i2 a3 = pot%fc3%atom(a1)%triplet(i)%i3 + u1 = u(:, a1) u2 = u(:, a2) u3 = u(:, a3) do i1 = 1, 3 do i2 = 1, 3 do i3 = 1, 3 v0(i1) = v0(i1) - m3(i1, i2, i3)*u2(i2)*u3(i3) + do i4 = 1, 3 + s3(i3, i4) = s3(i3, i4) + m3(i1, i2, i3)*u1(i1)*u2(i2)*pot%fc3%atom(a1)%triplet(i)%rv3(i4) / ss%volume / 6.0_r8 + end do end do end do end do end do v0 = v0*0.5_r8 - f3(:, a1) = v0 e3 = e3 - dot_product(v0, u(:, a1))/3.0_r8 end do end if @@ -236,7 +140,6 @@ subroutine energies_and_forces(pot, u, e2, e3, e4, ep, f2, f3, f4, fp) end do end do v0 = v0/6.0_r8 - f4(:, a1) = v0 e4 = e4 - dot_product(v0, u(:, a1))/4.0_r8 end do end if @@ -267,11 +170,6 @@ subroutine setup_potential_energy_differences(pot, uc, ss, fc2, fc3, fc4, mw, ve t0 = timer t1 = timer - if (verbosity .gt. 0) then - write (*, *) '' - write (*, *) 'PREPARING POTENTIAL ENERGY DIFFERENCES' - end if - call fc2%remap(uc, ss, pot%fc2) if (verbosity .gt. 0) then t1 = walltime() @@ -312,223 +210,217 @@ subroutine setup_potential_energy_differences(pot, uc, ss, fc2, fc3, fc4, mw, ve end if end subroutine -! !> remove longrange interactions -! subroutine potential_energy_difference(sim,uc,ss,fc,fct,fcf,Uref,mw,verbosity) -! !> force-displacement data -! type(lo_mdsim), intent(inout) :: sim -! !> unitcell -! type(lo_crystalstructure), intent(inout) :: uc -! !> supercell -! type(lo_crystalstructure), intent(inout) :: ss -! !> second order forceconstant -! type(lo_forceconstant_secondorder), intent(in) :: fc -! !> third order forceconstant -! type(lo_forceconstant_thirdorder), intent(in) :: fct -! !> fourth order forceconstant -! type(lo_forceconstant_fourthorder), intent(in) :: fcf -! !> reference energy -! real(flyt), intent(in) :: Uref -! !> mpi things -! type(lo_mpi_helper), intent(inout) :: mw -! !> how much to talk -! integer, intent(in) :: verbosity -! -! type(lo_forceconstant_secondorder) :: fcss -! type(lo_forceconstant_thirdorder) :: fctss -! type(lo_forceconstant_fourthorder) :: fcfss -! real(flyt), dimension(:,:,:,:), allocatable :: forceconstant -! real(flyt), dimension(:,:), allocatable :: fp,f2,f3,f4,de -! ! real(flyt), dimension(:,:), allocatable :: f,de -! ! real(flyt), dimension(3,3) :: m0,m1 -! ! real(flyt), dimension(3) :: v0 -! ! real(flyt) :: epot,epot_2,epot_3,epot_4,epot_dd -! ! integer :: a1,a2,t,u -! -! init: block -! real(flyt), dimension(3,3) :: m0,m1 -! real(flyt) :: t0,f0 -! integer :: a1,a2 -! if ( mw%talk ) then -! write(*,*) '' -! write(*,*) 'CALCULATING POTENTIAL ENERGY DIFFERENCES' -! endif -! ! Remap the forceconstants to the supercell -! call ss%classify('supercell',uc) -! call fc%remap(uc,ss,fcss) -! call fct%remap(uc,ss,fctss) -! call fcf%remap(uc,ss,fcfss) -! if ( mw%talk ) write(*,*) '... remapped forceconstants' -! ! Get the dipole-dipole forceconstant -! if ( fc%polar ) then -! lo_allocate(forceconstant(3,3,ss%na,ss%na)) -! call fc%supercell_longrange_dynamical_matrix_at_gamma(ss,forceconstant,1E-15_flyt) -! ! small sanity-check, just in case -! f0=0.0_flyt -! do a1=1,ss%na -! do a2=a1,ss%na -! m0=forceconstant(:,:,a1,a2) -! m1=transpose(forceconstant(:,:,a2,a1)) -! f0=f0+lo_frobnorm(m0-m1) -! enddo -! enddo -! f0=f0/(ss%na**2) -! if ( f0 .gt. lo_tol ) then -! write(*,*) 'ERROR, non-Hermitian electrostatic forceconstant: ',f0 -! write(*,*) 'If this keeps happening I should not hard-code the Ewald tolerance.' -! stop -! endif -! endif -! -! ! some space for energies and forces -! lo_allocate(de(sim%nt,5)) -! lo_allocate(fp(3,ss%na)) -! lo_allocate(f2(3,ss%na)) -! lo_allocate(f3(3,ss%na)) -! lo_allocate(f4(3,ss%na)) -! de=0.0_flyt -! fp=0.0_flyt -! f2=0.0_flyt -! f3=0.0_flyt -! f4=0.0_flyt -! end block init -! -! forceenergy: block -! real(flyt), dimension(3,3,3,3) :: m4 -! real(flyt), dimension(3,3,3) :: m3 -! real(flyt), dimension(3,3) :: m2 -! real(flyt), dimension(3) :: u1,u2,u3,u4,v0 -! real(flyt) :: energy -! integer :: a1,a2,a3,a4,i1,i2,i3,i4,i,j,k,l,t -! -! do t=1,sim%nt -! ! get the raw energy -! de(t,1)=sim%stat%potential_energy(t) -! -! ! secondorder energy, first the polar term (if applicable) -! energy=0.0_flyt -! if ( fc%polar ) then -! do a1=1,ss%na -! v0=0.0_flyt -! do a2=1,ss%na -! v0=v0+matmul(forceconstant(:,:,a2,a1),u(:,a2,t)) -! enddo -! energy=energy+dot_product(u(:,a1,t),v0)*0.5_flyt -! enddo -! endif -! ! then the pair term, always there -! do a1=1,ss%na -! v0=0.0_flyt -! do i1=1,fcss%atom(a1)%n -! a2=fcss%atom(a1)%pair(i1)%i2 -! m2=fcss%atom(a1)%pair(i1)%m -! v0=v0+matmul(m2,u(:,a2,t)) -! enddo -! energy=energy+dot_product(u(:,a1,t),v0)*0.5_flyt -! enddo -! de(t,2)=energy -! -! ! triplet term -! f3=0.0_flyt -! energy=0.0_flyt -! do a1=1,fcss%na -! v0=0.0_flyt -! do i=1,fctss%atom(a1)%n -! m3=fctss%atom(a1)%triplet(i)%m -! a2=fctss%atom(a1)%triplet(i)%i2 -! a3=fctss%atom(a1)%triplet(i)%i3 -! u2=u(:,a2,t) -! u3=u(:,a3,t) -! do i1=1,3 -! do i2=1,3 -! do i3=1,3 -! v0(i1)=v0(i1)-m3(i1,i2,i3)*u2(i2)*u3(i3) -! enddo -! enddo -! enddo -! enddo -! f3(:,a1)=v0*0.5_flyt -! energy=energy-dot_product(f3(:,a1),u(:,a1,t))/3.0_flyt -! enddo -! de(t,3)=energy -! -! ! quartet term -! f4=0.0_flyt -! energy=0.0_flyt -! do a1=1,fcfss%na -! v0=0.0_flyt -! do i=1,fcfss%atom(a1)%n -! m4=fcfss%atom(a1)%quartet(i)%m -! a2=fcfss%atom(a1)%quartet(i)%i2 -! a3=fcfss%atom(a1)%quartet(i)%i3 -! a4=fcfss%atom(a1)%quartet(i)%i4 -! u2=u(:,a2,t) -! u3=u(:,a3,t) -! u4=u(:,a4,t) -! do i1=1,3 -! do i2=1,3 -! do i3=1,3 -! do i4=1,3 -! v0(i1)=v0(i1)-m4(i1,i2,i3,i4)*u2(i2)*u3(i3)*u4(i4) -! enddo -! enddo -! enddo -! enddo -! enddo -! f4(:,a1)=v0/6.0_flyt -! energy=energy-dot_product(f4(:,a1),u(:,a1,t))/4.0_flyt -! enddo -! de(t,4)=energy -! enddo -! end block forceenergy -! -! if ( mw%talk ) then -! write(*,*) ' raw avg potential energy:',lo_mean(de(:,1)) -! write(*,*) ' E-E2:',lo_mean(de(:,1)-de(:,2)) -! write(*,*) ' E-E2-E3:',lo_mean(de(:,1)-de(:,2)-de(:,3)) -! write(*,*) ' E-E2-E3-E4:',lo_mean(de(:,1)-de(:,2)-de(:,3)-de(:,4)) -! endif -! -! -! !! Energy per atom -! !de=1000*de/sim%na -! ! -! !if ( mw%talk ) then -! !write(*,*) 'RAW:',lo_mean(de(:,1)),lo_stddev(de(:,1)) -! !write(*,*) 'RAW:',lo_mean(de(:,1)-de(:,3)),lo_stddev(de(:,1)-de(:,3)) -! !write(*,*) 'RAW:',lo_mean(de(:,1)-de(:,2)-de(:,3)),lo_stddev(de(:,1)-de(:,2)-de(:,3)) -! !write(*,*) 'RAW:',lo_mean(de(:,1)-de(:,2)-de(:,3)-de(:,4)),lo_stddev(de(:,1)-de(:,2)-de(:,3)-de(:,4)) -! !write(*,*) 'RAW:',lo_mean(de(:,1)-de(:,2)-de(:,3)-de(:,4)-de(:,5)),lo_stddev(de(:,1)-de(:,2)-de(:,3)-de(:,4)-de(:,5)) -! !u=open_file('out','outfile.U0') -! ! do t=1,sim%nt -! ! write(u,"(6(1X,E18.12))") de(t,:)/1000*sim%na,(de(t,1)-de(t,2)-de(t,3)-de(t,4)-de(t,5))/1000*sim%na -! ! enddo -! !close(u) -! !endif -! -! ! t0=walltime() -! ! call lo_progressbar_init() -! ! ! Subtract forces -! ! lo_allocate(f(3,ss%na)) -! ! do t=1,sim%nt -! ! ! calculate the long-range forces -! ! f=0.0_flyt -! ! do a1=1,ss%na -! ! do a2=1,ss%na -! ! v0=matmul(forceconstant(:,:,a1,a2),u(:,a2,t)) -! ! f(:,a1)=f(:,a1)-v0 -! ! enddo -! ! enddo -! ! ! sanity check that they add up to zero -! ! if ( abs(sum(f)) .gt. lo_sqtol ) then -! ! write(*,*) '' -! ! write(*,*) 'ERROR: dipole-dipole forces do not add up to zero!' -! ! stop -! ! endif -! ! ! subtract them -! ! sim%f(:,:,t)=sim%f(:,:,t)-f -! ! if( lo_trueNtimes(t,50,sim%nt) ) call lo_progressbar(' ... subtracting dipole-dipole forces',t,sim%nt) -! ! enddo -! ! call lo_progressbar(' ... subtracting dipole-dipole forces',sim%nt,sim%nt,walltime()-t0) -! end subroutine +!> Compute the thermodynamic corrections from the data +subroutine compute_realspace_thermo(pot, ss, sim, thermo, nblocks, mw, mem) + !> container for potential energy differences + class(lo_energy_differences), intent(in) :: pot + !> The supercell + type(lo_crystalstructure), intent(in) :: ss + !> The simulation + type(lo_mdsim), intent(in) :: sim + !> The thermodynamic helper + type(lo_thermodynamics), intent(inout) :: thermo + !> Number of blocks + integer, intent(in) :: nblocks + !> MPI + type(lo_mpi_helper), intent(inout) :: mw + !> memory tracker + type(lo_mem_helper), intent(inout) :: mem + + !> The stress difference between true and ifcs + real(r8), dimension(:, :, :), allocatable :: sdiff + !> The energy difference between true and ifcs + real(r8), dimension(:, :), allocatable :: ediff + + ! Allocate stuffs + call mem%allocate(ediff, [sim%nt, 4], persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%allocate(sdiff, [sim%nt, 6, 2], persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + ediff = 0.0_r8 + sdiff = 0.0_r8 + + ! Let's compute energies and stress differences + energy_computation: block + !> The stress contributions + real(r8), dimension(3, 3) :: s3 + !> The individual energy contributions + real(r8) :: e2, e3, e4, ep + !> The time + real(r8) :: t0 + !> Some integers + integer :: i, j, ntot, a, b + + ! For a nice progressbar, we count the number of configuration on the rank + ntot = 0 + do i=1, sim%nt + if (mod(i, mw%n) .eq. mw%r) ntot = ntot + 1 + end do + + t0 = walltime() + if (mw%talk) call lo_progressbar_init() + j = 0 + do i=1, sim%nt + if (mod(i, mw%n) .ne. mw%r) cycle + j = j + 1 + call pot%energies_and_forces(ss, sim%u(:, :, i), e2, e3, e4, ep, s3) + ! We store the energy differences + ediff(i, 1) = sim%stat%potential_energy(i) + ediff(i, 2) = sim%stat%potential_energy(i) - e2 - ep + ediff(i, 3) = sim%stat%potential_energy(i) - e2 - ep - e3 + ediff(i, 4) = sim%stat%potential_energy(i) - e2 - ep - e3 - e4 + + ! But also the stress differences, in Voigt notation + sdiff(i, :, 1) = lo_full_to_voigt_33(sim%stat%stress(:, :, i)) + sdiff(i, :, 2) = lo_full_to_voigt_33(sim%stat%stress(:, :, i) - s3) + if (mw%talk .and. lo_trueNtimes(i, 127, ntot)) then + call lo_progressbar(' ... computing energy from IFC', j, ntot, walltime() - t0) + end if + end do + if (mw%talk) then + call lo_progressbar(' ... computing energy from IFC', ntot, ntot, walltime() - t0) + end if + ! And reduce everything + call mw%allreduce('sum', ediff) + call mw%allreduce('sum', sdiff) + end block energy_computation + + averaging: block + !> Buffer for the stress tensor + real(r8), dimension(6, 2) :: stress_voigt + !> Buffer for the thermodynamic quantities + real(r8), dimension(2) :: F, S, Cv, U0 + !> Little buffers for the blocks + real(r8), dimension(:, :), allocatable :: buf, bufcv, bufstress + !> Some buffers: energy, inverse kbt blabla + real(r8) :: inverse_kbt, f0, f1, f2, blocksize, sqnm1 + !> Some integers + integer :: i, j, a, b, istart, iend + + if (mw%talk) write(*, *) '... computing cumulant corrections' + !> Let's get the inverse temperature + if (thermo%temperature .gt. 1E-5_r8) then + inverse_kbt = 1.0_r8/lo_kb_Hartree/thermo%temperature + else + inverse_kbt = 0.0_r8 + end if + + ! We need the length of each block for the block averaging + blocksize = real(sim%nt, r8) / real(nblocks, r8) + if (thermo%stochastic) then + call mem%allocate(buf, [2, nblocks], persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%allocate(bufcv, [2, nblocks], persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%allocate(bufstress, [6, nblocks], persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + buf = 0.0_r8 + bufcv = 0.0_r8 + bufstress = 0.0_r8 + ! For the stochastic, what we compute depends on the order included + do j=1, nblocks + ! Index for the block + istart = ceiling(blocksize*(j-1) + 1) + iend = min(ceiling(blocksize*j), sim%nt) + ! Now we compute the average for each block + if (thermo%fourthorder) then + f0 = lo_mean(ediff(istart:iend, 4)) + buf(1, j) = f0 + buf(2, j) = lo_mean((ediff(istart:iend, 3) - f0)**2) + else if (thermo%thirdorder) then + f0 = lo_mean(ediff(istart:iend, 3)) + buf(1, j) = f0 + buf(2, j) = lo_mean((ediff(istart:iend, 3) - f0)**2) + else + f0 = lo_mean(ediff(istart:iend, 2)) + buf(1, j) = f0 + buf(2, j) = lo_mean((ediff(istart:iend, 2) - f0)**2) + end if + + ! And the stress + if (thermo%fourthorder .or. thermo%thirdorder) then + do a=1, 6 + bufstress(a, j) = lo_mean(sdiff(istart:iend, a, 2)) + end do + else + do a=1, 6 + bufstress(a, j) = lo_mean(sdiff(istart:iend, a, 1)) + end do + end if + end do + ! First we get the U0 term + U0(1) = lo_mean(buf(1, :)) + U0(2) = sqrt(lo_mean((buf(1, :) - U0(1))**2)) + U0 = U0 / sim%na + ! Then the + + ! And the stress + do a=1, 6 + stress_voigt(a, 1) = lo_mean(bufstress(a, :)) + stress_voigt(a, 2) = lo_stddev(bufstress(a, :)) * sqnm1 + end do + + thermo%first_order%F = U0 + thermo%first_order%stress(:, :, 1) = thermo%first_order%stress(:, :, 1) + lo_voigt_to_full_33(stress_voigt(:, 1)) + thermo%first_order%stress(:, :, 2) = thermo%first_order%stress(:, :, 2) + lo_voigt_to_full_33(stress_voigt(:, 2)) + else + call mem%allocate(buf, [2, nblocks], persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%allocate(bufcv, [2, nblocks], persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%allocate(bufstress, [6, nblocks], persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + buf = 0.0_r8 + bufcv = 0.0_r8 + bufstress = 0.0_r8 + do j=1, nblocks + ! Index for the block + istart = ceiling(blocksize*(j-1) + 1) + iend = min(ceiling(blocksize*j), sim%nt) + ! Now we compute the average for each block + ! This is to get the U0 + f0 = lo_mean(ediff(istart:iend, 2)) + f1 = lo_mean(ediff(istart:iend, 1)) + buf(1, j) = f0 + ! This is to get the correction to the entropy + buf(2, j) = lo_mean((ediff(istart:iend, 2) - f0)**2) + ! This is to get the correction to the heat capacity + bufcv(1, j) = lo_mean((ediff(istart:iend, 1) - f1) * (ediff(istart:iend, 2) - f0)) + ! And the stress + do a=1, 6 + bufstress(a, j) = lo_mean(sdiff(istart:iend, a, 1)) + end do + end do + ! Something to normalize the block averaging + if (nblocks .eq. 1) then + sqnm1 = 1.0_r8 + else + sqnm1 = 1.0_r8 / sqrt(real(nblocks, r8) - 1.0_r8) + end if + ! First we get the U0 term + U0(1) = lo_mean(buf(1, :)) + U0(2) = lo_stddev(buf(1, :)) * sqnm1 + U0 = U0 / sim%na + + ! Now we need the entropy correction + S(1) = lo_mean(buf(2, :)) + S(2) = lo_stddev(buf(2, :)) * sqnm1 + S = 0.5_r8 * lo_kb_Hartree * S * inverse_kbt**2 / sim%na + + ! And the heat capacity correction + Cv(1) = lo_mean(bufcv(1, :)) + Cv(2) = lo_stddev(bufcv(1, :)) * sqnm1 + Cv = Cv * inverse_kbt**2 * lo_kb_Hartree / sim%na + + ! And the stress + do a=1, 6 + stress_voigt(a, 1) = lo_mean(bufstress(a, :)) + stress_voigt(a, 2) = lo_stddev(bufstress(a, :)) * sqnm1 + end do + + ! And we store the results + thermo%first_order%F = U0 + thermo%second_order%F(1) = -thermo%temperature * S(1) + thermo%second_order%F(2) = thermo%temperature * S(2) + thermo%first_order%U = U0 + thermo%second_order%S = S + thermo%second_order%Cv = Cv + thermo%first_order%stress(:,: , 1) = lo_voigt_to_full_33(stress_voigt(:, 1)) + thermo%first_order%stress(:,: , 2) = lo_voigt_to_full_33(stress_voigt(:, 2)) + end if + end block averaging +end subroutine end module diff --git a/src/anharmonic_free_energy/fourthorder.f90 b/src/anharmonic_free_energy/fourthorder.f90 new file mode 100644 index 00000000..812aece5 --- /dev/null +++ b/src/anharmonic_free_energy/fourthorder.f90 @@ -0,0 +1,479 @@ +module fourthorder +!! Compute the fourth order contribution to the anharmonic free energy +use konstanter, only: r8, lo_freqtol, lo_twopi, lo_imag, lo_kb_Hartree, lo_exitcode_param +use gottochblandat, only: walltime, lo_trueNtimes, lo_progressbar_init, lo_progressbar, lo_planck, & + lo_planck_deriv, lo_planck_secondderiv +use mpi_wrappers, only: lo_mpi_helper, lo_stop_gracefully +use lo_memtracker, only: lo_mem_helper +use type_qpointmesh, only: lo_qpoint_mesh, lo_fft_mesh +use type_crystalstructure, only: lo_crystalstructure +use type_forceconstant_fourthorder, only: lo_forceconstant_fourthorder +use type_phonon_dispersions, only: lo_phonon_dispersions +use lo_timetracker, only: lo_timer +use lo_fftgrid_helper, only: fft_fourth_grid_index + +implicit none +private + +public :: free_energy_fourthorder +public :: free_energy_fourthorder_secondorder + +contains +!> Calculate the fourth order free energy +subroutine free_energy_fourthorder(uc, fcf, qp, dr, temperature, df4, s4, cv4, quantum, mw, mem) + !> crystal structure + type(lo_crystalstructure), intent(in) :: uc + !> fourth order force constant + type(lo_forceconstant_fourthorder), intent(in) :: fcf + !> q-point mesh + class(lo_qpoint_mesh), intent(in) :: qp + !> dispersions + type(lo_phonon_dispersions), intent(in) :: dr + !> temperature + real(r8) :: temperature + !> free energies, entropy and heat capacity + real(r8), intent(out) :: df4, s4, cv4 + !> what to compute + logical, intent(in) :: quantum + !> mpi helper + type(lo_mpi_helper), intent(inout) :: mw + !> memory tracker + type(lo_mem_helper), intent(inout) :: mem + + !> Frequency scaled eigenvectors + complex(r8), dimension(:), allocatable :: egv1, egv2, egv3, egv4 + !> Helper for Fourier transform of psi3 + complex(r8), dimension(:), allocatable :: ptf, evp1, evp2, evp3 + !> Frequencies, bose-einstein occupation and scattering strength and some other buffer + real(r8) :: sig, om1, om2, om3, om4, n1, n2, n3, n4, psisq, f0, f1, f2, t0, prefactor + !> + real(r8) :: s1, s2, s3, mult, dn1, dn2, ddn1, ddn2, df0, ddf0 + !> The complex threephonon matrix element + complex(r8) :: c0 + !> Integers for do loops and counting + integer :: qi, q1, q2, q3, q4, b1, b2, b3, b4, i, ctr + + ! We start by allocating everything + call mem%allocate(ptf, dr%n_mode**4, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%allocate(evp1, dr%n_mode**2, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%allocate(evp2, dr%n_mode**3, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%allocate(evp3, dr%n_mode**4, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%allocate(egv1, dr%n_mode, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%allocate(egv2, dr%n_mode, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + + t0 = walltime() + + df4 = 0.0_r8 + s4 = 0.0_r8 + cv4 = 0.0_r8 + + ctr = 0 + do q1=1, qp%n_irr_point + do q2=1, qp%n_full_point + ctr = ctr + 1 + if (mod(ctr, mw%n) .ne. mw%r) cycle + + prefactor = qp%ip(q1)%integration_weight*qp%ap(q2)%integration_weight/uc%na + ! pre-transform the matrix element + call pretransform_phi4_first(fcf, qp%ip(q1)%r, qp%ap(q2)%r, ptf) + + do b1=1, dr%n_mode + om1 = dr%iq(q1)%omega(b1) + if (om1 .lt. lo_freqtol) cycle + egv1 = dr%iq(q1)%egv(:, b1)/sqrt(om1) + do b2=1, dr%n_mode + om2 = dr%aq(q2)%omega(b2) + if (om2 .lt. lo_freqtol) cycle + + egv2 = dr%aq(q2)%egv(:, b2)/sqrt(om2) + evp1 = 0.0_r8 + evp2 = 0.0_r8 + evp3 = 0.0_r8 + call zgerc(dr%n_mode, dr%n_mode, (1.0_r8, 0.0_r8), egv1, 1, egv1, 1, evp1, dr%n_mode) + call zgerc(dr%n_mode, dr%n_mode, (1.0_r8, 0.0_r8), egv2, 1, egv2, 1, evp2, dr%n_mode) + call zgeru(dr%n_mode**2, dr%n_mode**2, (1.0_r8, 0.0_r8), evp2, 1, evp1, 1, evp3, dr%n_mode**2) + evp3 = conjg(evp3) + psisq = real(dot_product(evp3, ptf), r8) + + if (quantum) then + ! Phonon occupation + n1 = lo_planck(temperature, om1) + n2 = lo_planck(temperature, om2) + ! First derivative with respect to temperature + dn1 = lo_planck_deriv(temperature, om1) + dn2 = lo_planck_deriv(temperature, om2) + ! Second derivative with respect to temperature + ddn1 = lo_planck_secondderiv(temperature, om1) + ddn2 = lo_planck_secondderiv(temperature, om2) + ! The free energy + f0 = (2.0_r8 * n1 + 1.0_r8) * (2.0_r8 * n2 + 1.0_r8) / 32.0_r8 + ! The entropy + df0 = 2.0_r8 * dn1 * (2.0_r8 * n2 + 1.0_r8) + (2.0_r8 * n1 + 1.0_r8) * 2.0_r8 * dn2 + df0 = df0 / 32.0_r8 + ddf0 = 2.0_r8 * ddn1 * (2.0_r8 * n2 + 1.0_r8) + 2.0_r8 * ddn2 * (2.0_r8 * n1 + 1.0_r8) + & + 8.0_r8 * dn1 * dn2 + ddf0 = ddf0 * temperature / 32.0_r8 + else + ! Much simpler in the classical case + ! Free energy + f0 = (lo_kb_Hartree*temperature)**2 / (om1*om2) / 8.0_r8 + ! Entropy + df0 = lo_kb_Hartree**2 * temperature / (om1*om2) / 4.0_r8 + ! Heat capacity + ddf0 = lo_kb_Hartree**2 * temperature / (om1*om2) / 4.0_r8 + end if + ! And we accumulate + df4 = df4 + f0 * psisq * prefactor + s4 = s4 - df0 * psisq * prefactor + cv4 = cv4 - ddf0 * psisq * prefactor + end do + end do + end do + if (mw%talk .and. lo_trueNtimes(q1, 127, qp%n_irr_point)) then + call lo_progressbar(' ... fourth order', q1, qp%n_irr_point, walltime() - t0) + end if + end do + ! For a nice progressbar + if (mw%talk) then + call lo_progressbar(' ... fourth order', qp%n_irr_point, qp%n_irr_point, walltime() - t0) + end if + ! Reduce on all ranks + call mw%allreduce('sum', df4) + call mw%allreduce('sum', s4) + call mw%allreduce('sum', cv4) + + ! And deallocate + call mem%deallocate(ptf, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%deallocate(evp1, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%deallocate(evp2, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%deallocate(evp3, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%deallocate(egv1, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%deallocate(egv2, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) +end subroutine + +!> Calculate the fourth order free energy +subroutine free_energy_fourthorder_secondorder(uc, fcf, qp, dr, temperature, fe4, s4, cv4, quantum, mw, mem) + !> crystal structure + type(lo_crystalstructure), intent(in) :: uc + !> fourth order force constant + type(lo_forceconstant_fourthorder), intent(in) :: fcf + !> q-point mesh + class(lo_qpoint_mesh), intent(in) :: qp + !> dispersions + type(lo_phonon_dispersions), intent(in) :: dr + !> temperature + real(r8) :: temperature + !> free energies, entropy and heat capacity + real(r8), intent(out) :: fe4, s4, cv4 + !> what to compute + logical, intent(in) :: quantum + !> mpi helper + type(lo_mpi_helper), intent(inout) :: mw + !> memory tracker + type(lo_mem_helper), intent(inout) :: mem + + !> For the smearing parameters + real(r8), dimension(:, :), allocatable :: sigsq + !> Frequency scaled eigenvectors + complex(r8), dimension(:), allocatable :: egv1, egv2, egv3, egv4 + !> Helper for Fourier transform of psi3 + complex(r8), dimension(:), allocatable :: ptf, evp1, evp2, evp3 + !> Phonon occupations + real(r8), dimension(4) :: n, dn, ddn + !> Frequencies, bose-einstein occupation and scattering strength and some other buffer + real(r8) :: sigma, om1, om2, om3, om4, psisq, f0, f1, f2, f3, t0, prefactor + !> + real(r8) :: s1, s2, s3, mult, df0, ddf0, sig, sig1, sig2, sig3, sig4 + !> The phonon occupation plus 1 + real(r8) :: np1, np2, np3, np4 + !> The multiplicities + real(r8) :: m0, m1, m2, m3 + !> The complex threephonon matrix element + complex(r8) :: c0 + !> Integers for do loops and counting + integer :: qi, q1, q2, q3, q4, b1, b2, b3, b4, i, ctr + !> The dimension of the q-grid + integer, dimension(3) :: dims + + ! We start by allocating everything + call mem%allocate(ptf, dr%n_mode**4, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%allocate(evp1, dr%n_mode**2, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%allocate(evp2, dr%n_mode**3, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%allocate(evp3, dr%n_mode**4, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%allocate(egv1, dr%n_mode, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%allocate(egv2, dr%n_mode, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%allocate(egv3, dr%n_mode, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%allocate(egv4, dr%n_mode, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%allocate(sigsq, [qp%n_irr_point, dr%n_mode], persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + + t0 = walltime() + + select type (qp) + class is (lo_fft_mesh) + dims = qp%griddensity + class default + call lo_stop_gracefully(['This routine only works with FFT meshes'], lo_exitcode_param, __FILE__, __LINE__) + end select + + fe4 = 0.0_r8 + s4 = 0.0_r8 + cv4 = 0.0_r8 + + ! First we compute the broadening parameter for each modes + sigsq = 0.0_r8 + do q1=1, qp%n_irr_point + do b1=1, dr%n_mode + sigsq(q1, b1) = qp%smearingparameter(dr%iq(q1)%vel(:, b1), dr%default_smearing(b1), 1.0_r8)**2 + end do + end do + + n = 0.0_r8 + dn = 0.0_r8 + ddn = 0.0_r8 + + do q1=1, qp%n_irr_point + do q2=1, qp%n_full_point + do q3=1, qp%n_full_point + ctr = ctr + 1 + if (mod(ctr, mw%n) .ne. mw%r) cycle + q4 = fft_fourth_grid_index(qp%ip(q1)%full_index, q2, q3, dims) + + if (q3 .lt. q2) cycle + if (q4 .lt. q3) cycle + + ! Prefactors to account for equivalent points + if (q2 .eq. q3 .and. q3 .eq. q4) then + m0 = 1.0_r8 + m1 = 1.0_r8 + m2 = 1.0_r8 + m3 = 1.0_r8 + else if ((q2 .ne. q3 .and. q3 .eq. q4) .or. & + (q3 .ne. q2 .and. q2 .eq. q4) .or. & + (q4 .ne. q2 .and. q2 .eq. q3)) then + m0 = 3.0_r8 + m1 = 1.0_r8 + m2 = 1.0_r8 + m3 = 1.0_r8 + else + m0 = 6.0_r8 + m1 = 2.0_r8 + m2 = 2.0_r8 + m3 = 2.0_r8 + end if + + prefactor = qp%ip(q1)%integration_weight*qp%ap(q2)%integration_weight*qp%ap(q2)%integration_weight/uc%na + ! pre-transform the matrix element + call pretransform_phi4(fcf, qp%ap(q2)%r, qp%ap(q3)%r, qp%ap(q4)%r, ptf) + + do b1=1, dr%n_mode + ! Get first phonon + om1 = dr%iq(q1)%omega(b1) + if (om1 .lt. lo_freqtol) cycle + n(1) = lo_planck(temperature, om1) + dn(1) = lo_planck_deriv(temperature, om1) + ddn(1) = lo_planck_secondderiv(temperature, om1) + egv1 = dr%iq(q1)%egv(:, b1)/sqrt(om1) + do b2=1, dr%n_mode + ! Get second phonon + om2 = dr%aq(q2)%omega(b2) + if (om2 .lt. lo_freqtol) cycle + n(2) = lo_planck(temperature, om2) + dn(2) = lo_planck_deriv(temperature, om2) + ddn(2) = lo_planck_secondderiv(temperature, om2) + egv2 = dr%aq(q2)%egv(:, b2)/sqrt(om2) + + ! Multiply first and second phonon + evp1 = 0.0_r8 + call zgeru(dr%n_mode, dr%n_mode, (1.0_r8, 0.0_r8), egv2, 1, egv1, 1, evp1, dr%n_mode) + do b3=1, dr%n_mode + ! Get third phonon + om3 = dr%aq(q3)%omega(b3) + if (om3 .lt. lo_freqtol) cycle + n(3) = lo_planck(temperature, om3) + dn(3) = lo_planck_deriv(temperature, om3) + ddn(3) = lo_planck_secondderiv(temperature, om3) + egv3 = dr%aq(q3)%egv(:, b3)/sqrt(om3) + + ! Project on third phonon + evp2 = 0.0_r8 + call zgeru(dr%n_mode, dr%n_mode**2, (1.0_r8, 0.0_r8), egv3, 1, evp1, 1, evp2, dr%n_mode) + do b4=1, dr%n_mode + ! Get fourth phonon + om4 = dr%aq(q4)%omega(b4) + if (om4 .lt. lo_freqtol) cycle + n(4) = lo_planck(temperature, om4) + dn(4) = lo_planck_deriv(temperature, om4) + ddn(4) = lo_planck_secondderiv(temperature, om4) + egv4 = dr%aq(q4)%egv(:, b4)/sqrt(om4) + + ! Project on fourth phonon + evp3 = 0.0_r8 + call zgeru(dr%n_mode, dr%n_mode**3, (1.0_r8, 0.0_r8), egv4, 1, evp2, 1, evp3, dr%n_mode) + evp3 = conjg(evp3) + + ! Compute the scattering matrix element + c0 = dot_product(evp3, ptf) + psisq = abs(c0*conjg(c0))*prefactor + + if (quantum) then + ! Phonon occupation + np1 = n(1) + 1.0_r8 + np2 = n(2) + 1.0_r8 + np3 = n(3) + 1.0_r8 + np4 = n(4) + 1.0_r8 + + ! We get the broadening parameter + sig1 = sigsq(q1, b1) + sig2 = sigsq(qp%ap(q2)%irreducible_index, b2) + sig3 = sigsq(qp%ap(q3)%irreducible_index, b3) + sig4 = sigsq(qp%ap(q4)%irreducible_index, b3) + sig = sqrt(sig1 + sig2 + sig3 + sig4) + + f1 = (np1*np2*np3*np4 - n(1)*n(2)*n(3)*n(4)) / real(1.0_r8/(om1+om2+om3+om4+lo_imag*sig), r8) + f2 = 4.0_r8*(n(1)*np2*np3*np4 - np1*n(2)*n(3)*n(4)) * real(1.0/(-om1+om2+om3+om4 + lo_imag*sig), r8) + f3 = 3.0_r8*(n(1)*n(2)*(n(3)+n(4)+1.0_r8) - n(3)*n(4)*(n(1)+n(2)+1.0_r8))*real(1.0/(om1+om2-om3-om4 + lo_imag*sig), r8) + + f0 = (f1 + f2 + f3) / 768.0_r8 + else + ! Much simpler in the classical case + ! Free energy + f0 = (lo_kb_Hartree*temperature)**3 / (om1*om2*om3*om4) / 48.0_r8 + ! Entropy + df0 = lo_kb_Hartree**3*temperature**2 / (om1*om2*om3*om4) / 16.0_r8 + ! Heat capacity + ddf0 = lo_kb_Hartree**3*temperature**2 / (om1*om2*om3*om4) / 8.0_r8 + end if + ! And we accumulate + fe4 = fe4 - f0 * psisq + s4 = s4 + df0 * psisq + cv4 = cv4 + ddf0 * psisq + end do + end do + end do + end do + end do + end do + if (mw%talk .and. lo_trueNtimes(q1, 127, qp%n_irr_point)) then + call lo_progressbar(' ... fourth order', q1, qp%n_irr_point, walltime() - t0) + end if + end do + ! For a nice progressbar + if (mw%talk) then + call lo_progressbar(' ... fourth order', qp%n_irr_point, qp%n_irr_point, walltime() - t0) + end if + ! Reduce on all ranks + call mw%allreduce('sum', fe4) + call mw%allreduce('sum', s4) + call mw%allreduce('sum', cv4) + + ! And deallocate memory + call mem%deallocate(ptf, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%deallocate(evp1, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%deallocate(evp2, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%deallocate(evp3, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%deallocate(egv1, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%deallocate(egv2, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%deallocate(egv3, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%deallocate(egv4, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) +end subroutine + +!> Get the Fourier transform of the fourth order matrix element +subroutine pretransform_phi4_first(fcf, q1, q2, ptf) + !> fourth order forceconstant + type(lo_forceconstant_fourthorder), intent(in) :: fcf + !> q-vectors + real(r8), dimension(3), intent(in) :: q1, q2 + !> flattened, pretransformed matrix element + complex(r8), dimension(:), intent(out) :: ptf + + integer :: i, j, k, l, m + + complex(r8) :: expiqr + real(r8), dimension(3) :: rv2, rv3, rv4 + real(r8) :: iqr + integer :: a1, a2, a3, a4, ia, ib, ic, id, q, nb + + nb = fcf%na*3 + ptf = 0.0_r8 + do a1 = 1, fcf%na + do q = 1, fcf%atom(a1)%n + a2 = fcf%atom(a1)%quartet(q)%i2 + a3 = fcf%atom(a1)%quartet(q)%i3 + a4 = fcf%atom(a1)%quartet(q)%i4 + + rv2 = fcf%atom(a1)%quartet(q)%lv2 + rv3 = fcf%atom(a1)%quartet(q)%lv3 + rv4 = fcf%atom(a1)%quartet(q)%lv4 + + iqr = -dot_product(q1, rv2) + dot_product(q2, rv3) - dot_product(q2, rv4) + iqr = iqr*lo_twopi + expiqr = cmplx(cos(iqr), sin(iqr), r8) + do l = 1, 3 + do k = 1, 3 + do j = 1, 3 + do i = 1, 3 + ia = (a1 - 1)*3 + i + ib = (a2 - 1)*3 + j + ic = (a3 - 1)*3 + k + id = (a4 - 1)*3 + l + ! Now for the grand flattening scheme, consistent with the zgeru operations above. + m = (ia - 1)*nb*nb*nb + (ib - 1)*nb*nb + (ic - 1)*nb + id + ptf(m) = ptf(m) + fcf%atom(a1)%quartet(q)%mwm(i, j, k, l)*expiqr + end do + end do + end do + end do + end do + end do +end subroutine + +!> Do half the transform to q-space +pure subroutine pretransform_phi4(fcf, q2, q3, q4, ptf) + !> Fourth order forceconstant + class(lo_forceconstant_fourthorder), intent(in) :: fcf + !> The q-vectors, without the 2pi + real(r8), dimension(3), intent(in) :: q2, q3, q4 + !> Flattened, pre-transformed matrix element + complex(r8), dimension(:), intent(out) :: ptf + + integer :: i, j, k, l, m + + complex(r8) :: expiqr + real(r8), dimension(3) :: rv2, rv3, rv4 + real(r8) :: iqr + integer :: a1, a2, a3, a4, ia, ib, ic, id, q, nb + + nb = fcf%na*3 + ptf = 0.0_r8 + do a1 = 1, fcf%na + do q = 1, fcf%atom(a1)%n + a2 = fcf%atom(a1)%quartet(q)%i2 + a3 = fcf%atom(a1)%quartet(q)%i3 + a4 = fcf%atom(a1)%quartet(q)%i4 + + rv2 = fcf%atom(a1)%quartet(q)%lv2 + rv3 = fcf%atom(a1)%quartet(q)%lv3 + rv4 = fcf%atom(a1)%quartet(q)%lv4 + + iqr = dot_product(q2, rv2) + dot_product(q3, rv3) + dot_product(q4, rv4) + iqr = -iqr*lo_twopi + expiqr = cmplx(cos(iqr), sin(iqr), r8) + do l = 1, 3 + do k = 1, 3 + do j = 1, 3 + do i = 1, 3 + ia = (a1 - 1)*3 + i + ib = (a2 - 1)*3 + j + ic = (a3 - 1)*3 + k + id = (a4 - 1)*3 + l + ! Now for the grand flattening scheme, consistent with the zgeru operations. + m = (ia - 1)*nb*nb*nb + (ib - 1)*nb*nb + (ic - 1)*nb + id + ptf(m) = ptf(m) + fcf%atom(a1)%quartet(q)%mwm(i, j, k, l)*expiqr + end do + end do + end do + end do + end do + end do +end subroutine +end module diff --git a/src/anharmonic_free_energy/lo_thermodynamic_helpers.f90 b/src/anharmonic_free_energy/lo_thermodynamic_helpers.f90 new file mode 100644 index 00000000..8550867e --- /dev/null +++ b/src/anharmonic_free_energy/lo_thermodynamic_helpers.f90 @@ -0,0 +1,125 @@ +#include "precompilerdefinitions" +module lo_thermodynamic_helpers +use konstanter, only: r8, lo_huge +use gottochblandat, only: lo_chop +use type_crystalstructure, only: lo_crystalstructure +use type_symmetryoperation, only: lo_operate_on_secondorder_tensor + +implicit none +private +public :: lo_thermodynamics +public :: lo_symmetrize_stress +public :: lo_full_to_voigt +public :: lo_full_to_voigt_33 +public :: lo_voigt_to_full_33 + +type lo_thermodynamic_contribution + ! The different contributions. First dimension is the result, second one the uncertainty + real(r8), dimension(2) :: F=0.0_r8 + real(r8), dimension(2) :: U=0.0_r8 + real(r8), dimension(2) :: S=0.0_r8 + real(r8), dimension(2) :: Cv=0.0_r8 + real(r8), dimension(3, 3, 2) :: stress=0.0_r8 +end type + +!> A container for all thermodynamic results +type lo_thermodynamics + !> The temperature at which everything is evaluated + real(r8) :: temperature=-lo_huge + ! The things to hold results + type(lo_thermodynamic_contribution) :: harmonic + type(lo_thermodynamic_contribution) :: first_order + type(lo_thermodynamic_contribution) :: second_order + type(lo_thermodynamic_contribution) :: threephonon + type(lo_thermodynamic_contribution) :: fourphonon + !> The thermal expansion + real(r8), dimension(3, 3) :: alpha + !> Is it a stochastic simulation ? + logical :: stochastic = .false. + !> Do we have third order ? + logical :: thirdorder = .false. + !> Do we have fourth order ? + logical :: fourthorder = .false. +end type + +contains +! Symmetrize 3x3 tensors +subroutine lo_symmetrize_stress(m, uc) + !> The input matrix + real(r8), dimension(3, 3), intent(inout) :: m + !> The unitcell + type(lo_crystalstructure), intent(in) :: uc + + real(r8), dimension(3, 3) :: tmp + integer :: iop + + tmp = 0.0_r8 + do iop = 1, uc%sym%n + tmp = tmp + lo_operate_on_secondorder_tensor(uc%sym%op(iop), m) + end do + m = tmp / real(uc%sym%n, r8) + m = lo_chop(m, sum(abs(m))*1e-6_r8) +end subroutine + +! Go from full 3x3 real space to 6 voigt notation +function lo_full_to_voigt(i, j) result(k) + !> Inputs + integer, intent(in) :: i + integer, intent(in) :: j + + integer :: k + + integer, dimension(2) :: d + k = 0 + if (i < j) then + d = [i, j] + else + d = [j, i] + end if + if (d(1) .eq. d(2)) k = d(1) + if (d(1) .eq. 1 .and. d(2) .eq. 2) k = 6 + if (d(1) .eq. 1 .and. d(2) .eq. 3) k = 5 + if (d(1) .eq. 2 .and. d(2) .eq. 3) k = 4 +end function + +!> Transform a 3x3 tensor in full representation into its Voigt representation +function lo_full_to_voigt_33(mi) result(mo) + !> The input tensor in full notation + real(r8), dimension(3, 3), intent(in) :: mi + !> The output vector in Voigt notation + real(r8), dimension(6) :: mo + + integer :: i, j + + mo = 0.0_r8 + do i=1, 3 + do j=i, 3 + if (i .eq. j) then + mo = mi(i, j) + else + mo = 0.5_r8 * (mi(i, j) + mi(j, i)) + end if + end do + end do +end function + +!> Transform a vector in Voigt notation into it's 3x3 full representation +function lo_voigt_to_full_33(mi) result(mo) + !> The input tensor in full notation + real(r8), dimension(6), intent(in) :: mi + !> The output vector in Voigt notation + real(r8), dimension(3, 3) :: mo + + integer :: i, j, k + + mo = 0.0_r8 + do i=1, 3 + do j=i, 3 + k = lo_full_to_voigt(i, j) + mo(i, j) = mi(k) + mo(j, i) = mi(k) + end do + end do +end function + +end module diff --git a/src/anharmonic_free_energy/main.f90 b/src/anharmonic_free_energy/main.f90 index f815e238..99f8b92f 100644 --- a/src/anharmonic_free_energy/main.f90 +++ b/src/anharmonic_free_energy/main.f90 @@ -1,8 +1,7 @@ program anharmonic_free_energy !!{!src/anharmonic_free_energy/manual.md!} -use konstanter, only: r8, lo_Hartree_to_eV, lo_kb_Hartree, lo_pressure_HartreeBohr_to_GPa -use gottochblandat, only: open_file, walltime, lo_linspace, lo_progressbar_init, lo_progressbar, tochar, & - lo_does_file_exist, lo_mean, lo_stddev +use konstanter, only: r8, lo_Hartree_to_eV, lo_kb_Hartree, lo_pressure_HartreeBohr_to_GPa, lo_status +use gottochblandat, only: open_file, walltime, lo_trace use mpi_wrappers, only: lo_mpi_helper use lo_memtracker, only: lo_mem_helper use lo_timetracker, only: lo_timer @@ -10,15 +9,13 @@ program anharmonic_free_energy use type_forceconstant_secondorder, only: lo_forceconstant_secondorder use type_forceconstant_thirdorder, only: lo_forceconstant_thirdorder use type_forceconstant_fourthorder, only: lo_forceconstant_fourthorder -use type_mdsim, only: lo_mdsim -use type_qpointmesh, only: lo_qpoint_mesh, lo_generate_qmesh, lo_read_qmesh_from_file, lo_fft_mesh +use type_qpointmesh, only: lo_qpoint_mesh, lo_generate_qmesh use type_phonon_dispersions, only: lo_phonon_dispersions -use lo_phonon_bandstructure_on_path, only: lo_phonon_bandstructure -use type_phonon_dos, only: lo_phonon_dos use options, only: lo_opts -use energy, only: perturbative_anharmonic_free_energy -use epot, only: lo_energy_differences +use thirdorder, only: free_energy_thirdorder, elastic_thirdorder +use fourthorder, only: free_energy_fourthorder +use lo_thermodynamic_helpers, only: lo_thermodynamics, lo_symmetrize_stress implicit none @@ -26,18 +23,13 @@ program anharmonic_free_energy type(lo_forceconstant_secondorder) :: fc type(lo_forceconstant_thirdorder) :: fct type(lo_forceconstant_fourthorder) :: fcf -type(lo_phonon_dispersions) :: dr type(lo_crystalstructure) :: uc -class(lo_qpoint_mesh), allocatable :: qp type(lo_mpi_helper) :: mw type(lo_mem_helper) :: mem type(lo_timer) :: tmr -type(lo_mdsim) :: sim -real(r8), dimension(3, 5) :: cumulant +type(lo_thermodynamics) :: thermo real(r8) :: timer_init, timer_total -real(r8) :: U0, U1, energy_unit_factor -logical :: havehighorder ! Init MPI, timers and options call mw%init() @@ -46,13 +38,26 @@ program anharmonic_free_energy call opts%parse() call tmr%start() -! set up all possible meshes and get all dispersions init: block - integer :: t, u - + call mw%init() ! only be verbose on the first rank if (.not. mw%talk) opts%verbosity = -10 + call tmr%start() + + if (mw%talk) then + write(*, *) 'ANHARMONIC FREE ENERGY' + write(*, *) 'Recap of the parameters governing the calculation' + write(*, *) '' + write(*, '(1X,A40,F20.12)') 'Temperature ', opts%temperature + write(*, '(1X,A40,L3)') 'Quantum limit ', opts%quantum + write(*, '(1X,A40,I4,I4,I4)') 'Q-point grid Harmonic ', opts%qgh + write(*, '(1X,A40,I4,I4,I4)') 'Third order q-point grid ', opts%qg3ph + write(*, '(1X,A40,I4,I4,I4)') 'Fourth order q-point grid ', opts%qg4ph + write(*, *) '' + end if + if (mw%talk) write(*, *) 'INITIALIZATION' + if (mw%talk) write(*, *) '... reading input files' ! Read structure call uc%readfromfile('infile.ucposcar', verbosity=opts%verbosity) call uc%classify('wedge', timereversal=.true.) @@ -62,23 +67,46 @@ program anharmonic_free_energy call fc%readfromfile(uc, 'infile.forceconstant', mem, verbosity=-1) if (mw%talk) write (*, *) '... read second order forceconstant' - if (opts%thirdorder) call fct%readfromfile(uc, 'infile.forceconstant_thirdorder') - if (opts%fourthorder) call fcf%readfromfile(uc, 'infile.forceconstant_fourthorder') - havehighorder = .false. - if (opts%thirdorder .or. opts%fourthorder) havehighorder = .true. + if (.not. opts%nothirdorder) then + call fct%readfromfile(uc, 'infile.forceconstant_thirdorder') + if (mw%talk) write (*, *) '... read third order forceconstant' + end if + if (.not. opts%nofourthorder) then + call fcf%readfromfile(uc, 'infile.forceconstant_fourthorder') + if (mw%talk) write (*, *) '... read fourth order forceconstant' + end if call tmr%tock('reading input') - ! Get a q-mesh for the integrations. Always an FFT mesh. - if (mw%talk) write (*, *) '... generating q-mesh' - call lo_generate_qmesh(qp, uc, opts%qgrid, 'fft', timereversal=.true., headrankonly=.false., mw=mw, mem=mem, verbosity=opts%verbosity) + timer_init = walltime() - timer_init + + thermo%temperature = opts%temperature + thermo%thirdorder = .not. opts%nothirdorder + thermo%fourthorder = .not. opts%nofourthorder +end block init + +latdyn: block + !> The phonon dispersion relation + type(lo_phonon_dispersions) :: dr + !> The qpoint mesh + class(lo_qpoint_mesh), allocatable :: qp + !> Some stuffs + real(r8) :: temperature + !> Some integers for do loops + integer :: i + + if (mw%talk) then + write(*, *) '' + write(*, *) 'HARMONIC CONTRIBUTION' + end if - ! Dispersions for everyone! + if (mw%talk) write(*, *) '... generating q-mesh' + call lo_generate_qmesh(qp, uc, opts%qgh, 'fft', timereversal=.true., & + headrankonly=.false., mw=mw, mem=mem, verbosity=opts%verbosity) + if (mw%talk) write(*, *) '... generating harmonic dispersion' call dr%generate(qp, fc, uc, mw=mw, mem=mem, verbosity=opts%verbosity) - if (mw%talk) write (*, *) '... got the full dispersion relations' - call tmr%tock('harmonic properties') - ! Check for imaginary modes right away + ! Little sanity check if (dr%omega_min .lt. 0.0_r8) then ! Dump the free energies if (mw%talk) then @@ -87,163 +115,192 @@ program anharmonic_free_energy call mw%destroy() stop end if - timer_init = walltime() - timer_init - -end block init - -! We start with the potential energy terms since those are much faster -epotthings: block - type(lo_energy_differences) :: pot - type(lo_crystalstructure) :: ss - - real(r8), dimension(:, :), allocatable :: f2, f3, f4, fp - real(r8), dimension(:, :), allocatable :: ediff - - real(r8) :: e2, e3, e4, ep, inverse_kbt - integer :: i - call ss%readfromfile('infile.ssposcar') - call ss%classify('supercell', uc) - call pot%setup(uc, ss, fc, fct, fcf, mw, opts%verbosity + 1) + temperature = opts%temperature - ! Fetch simulation data from file - if (lo_does_file_exist('infile.sim.hdf5')) then - call sim%read_from_hdf5('infile.sim.hdf5', verbosity=opts%verbosity + 2, stride=-1) + if (mw%talk) write(*, *) '... computing thermodynamic properties with harmonic dispersion' + ! We start by computing everything we can from the harmonic phonons + if (opts%quantum) then + thermo%harmonic%F(1) = dr%phonon_free_energy(temperature) + thermo%harmonic%S(1) = dr%phonon_entropy(temperature) + thermo%harmonic%U(1) = thermo%harmonic%F(1) + temperature * thermo%harmonic%S(1) + thermo%harmonic%Cv(1) = dr%phonon_cv(temperature) + ! call dr%phonon_kinetic_stress(qp, uc, temperature, thermo%harmonic%stress(:, :, 1)) else - call sim%read_from_file(verbosity=opts%verbosity + 2, stride=1, magnetic=.false., dielectric=.false., nrand=-1, mw=mw) + thermo%harmonic%F(1) = dr%phonon_free_energy_classical(temperature) + thermo%harmonic%U(1) = 3.0_r8 * lo_kb_Hartree * temperature + thermo%harmonic%S(1) = (thermo%harmonic%U(1) - thermo%harmonic%F(1)) / temperature + thermo%harmonic%Cv(1) = 3.0_r8 * lo_kb_Hartree + thermo%harmonic%stress = 0.0_r8 + ! do i=1, 3 + ! thermo%harmonic%stress(i, i, 1) = lo_kb_Hartree * temperature * uc%na / uc%volume + ! end do end if + ! Usually not needed here, but always a good idea to clean + ! call lo_symmetrize_stress(thermo%harmonic%stress(:, :, 1), uc) + + ! If we have third order IFC, might as well compute elastic things + ! if (opts%thirdorder) then + ! if (mw%talk) write(*, *) '... computing third order contribution to elastic properties' + + ! call elastic_thirdorder(uc, fc, fct, qp, dr, opts%temperature, thermo%threephonon%stress(:, :, 1), & + ! thermo%alpha, opts%quantum, mw, mem) + ! ! Now we symmetrize + ! call lo_symmetrize_stress(thermo%threephonon%stress(:, :, 1), uc) + ! call lo_symmetrize_stress(thermo%alpha, uc) + ! end if + call tmr%tock('harmonic properties') +end block latdyn - allocate (f2(3, ss%na)) - allocate (f3(3, ss%na)) - allocate (f4(3, ss%na)) - allocate (fp(3, ss%na)) - - ! Calculate the baseline energy - allocate (ediff(sim%nt, 5)) - ediff = 0.0_r8 - - do i = 1, sim%nt - if (mod(i, mw%n) .ne. mw%r) cycle - call pot%energies_and_forces(sim%u(:, :, i), e2, e3, e4, ep, f2, f3, f4, fp) - ediff(i, 1) = sim%stat%potential_energy(i) - ediff(i, 2) = sim%stat%potential_energy(i) - e2 - ediff(i, 3) = sim%stat%potential_energy(i) - e2 - ep - ediff(i, 4) = sim%stat%potential_energy(i) - e2 - ep - e3 - ediff(i, 5) = sim%stat%potential_energy(i) - e2 - ep - e3 - e4 - end do - call mw%allreduce('sum', ediff) - - if (sim%temperature_thermostat .gt. 1E-5_r8) then - inverse_kbt = 1.0_r8/lo_kb_Hartree/sim%temperature_thermostat - else - inverse_kbt = 0.0_r8 - end if +! Skipping cumulant/real-space corrections - only computing phonon contributions - ! Compute the first and second order cumulants - do i = 1, 5 - cumulant(1, i) = lo_mean(ediff(:, i)) - cumulant(2, i) = lo_mean((ediff(:, i) - cumulant(1, i))**2) - cumulant(2, i) = cumulant(2, i)*inverse_kbt*0.5_r8 - cumulant(3, i) = lo_mean((ediff(:, i) - cumulant(1, i))**3) - cumulant(3, i) = cumulant(3, i)*inverse_kbt**2/6.0_r8 - end do - ! And normalize it to be per atom - cumulant = cumulant/real(ss%na, r8) +latdyn3ph: block + !> The phonon dispersion relation + type(lo_phonon_dispersions) :: dr + !> The qpoint mesh + class(lo_qpoint_mesh), allocatable :: qp + !> The third order contribution + real(r8) :: fe3, s3, cv3 - if (mw%talk) then - write (*, *) 'Temperature (K) (from infile.meta): ', sim%temperature_thermostat - write (*, *) 'Potential energy:' - write (*, "(1X,A,E21.14,1X,A,F21.14)") ' input: ', cumulant(1, 1)*lo_Hartree_to_eV, ' upper bound:', cumulant(2, 1)*lo_Hartree_to_eV - write (*, "(1X,A,E21.14,1X,A,F21.14)") ' E-fc2: ', cumulant(1, 2)*lo_Hartree_to_eV, ' upper bound:', cumulant(2, 2)*lo_Hartree_to_eV - write (*, "(1X,A,E21.14,1X,A,F21.14)") ' E-fc2-polar: ', cumulant(1, 3)*lo_Hartree_to_eV, ' upper bound:', cumulant(2, 3)*lo_Hartree_to_eV - if (opts%thirdorder) then - write (*, "(1X,A,E21.14,1X,A,F21.14)") ' E-fc2-polar-fc3: ', cumulant(1, 4)*lo_Hartree_to_eV, ' upper bound:', cumulant(2, 4)*lo_Hartree_to_eV - end if - if (opts%fourthorder) then - write (*, "(1X,A,E21.14,1X,A,F21.14)") ' E-fc2-polar-fc3-fc4: ', cumulant(1, 5)*lo_Hartree_to_eV, ' upper bound:', cumulant(2, 5)*lo_Hartree_to_eV + + if (.not. opts%nothirdorder) then + if (mw%talk) then + write(*, *) '' + write(*, *) 'THREE PHONONS CONTRIBUTION' end if + + if (mw%talk) write(*, *) '... generating q-mesh' + call lo_generate_qmesh(qp, uc, opts%qg3ph, 'fft', timereversal=.true., & + headrankonly=.false., mw=mw, mem=mem, verbosity=opts%verbosity) + if (mw%talk) write(*, *) '... generating harmonic dispersion' + call dr%generate(qp, fc, uc, mw=mw, mem=mem, verbosity=opts%verbosity) + + call free_energy_thirdorder(uc, fct, qp, dr, opts%temperature, fe3, s3, cv3, opts%quantum, mw, mem) + thermo%threephonon%F(1) = fe3 + thermo%threephonon%S(1) = s3 + thermo%threephonon%U(1) = (fe3 + opts%temperature * s3) + thermo%threephonon%Cv(1) = cv3 end if -end block epotthings + call tmr%tock('three-phonon') -! Calculate the actual free energy -getenergy: block - real(r8) :: f_ph, ah3, ah4, fe2_1, fe2_2, fe3_1, fe3_2, fe4_1, fe4_2, pref - integer :: u - character(len=1000) :: opf +end block latdyn3ph - ! Some heuristics to figure out what the temperature is. - if (opts%quantum) then - f_ph = dr%phonon_free_energy(sim%temperature_thermostat) - else - f_ph = dr%phonon_free_energy_classical(sim%temperature_thermostat) - end if +latdyn4ph: block + !> The phonon dispersion relation + type(lo_phonon_dispersions) :: dr + !> The qpoint mesh + class(lo_qpoint_mesh), allocatable :: qp + !> The third order contribution + real(r8) :: fe4, s4, cv4 - if (havehighorder) then - select type (qp); type is (lo_fft_mesh) - call perturbative_anharmonic_free_energy(uc, fct, fcf, qp, dr, sim%temperature_thermostat, ah3, ah4, & - opts%fourthorder, opts%quantum, mw, mem, opts%verbosity + 1) - end select - else - ah3 = 0.0_r8 - ah4 = 0.0_r8 - end if + if (.not. opts%nofourthorder) then + if (mw%talk) then + write(*, *) '' + write(*, *) 'FOUR PHONONS CONTRIBUTION' + end if - if (opts%stochastic) then - pref = -1.0_r8 - else - pref = 1.0_r8 + if (mw%talk) write(*, *) '... generating q-mesh' + call lo_generate_qmesh(qp, uc, opts%qg4ph, 'fft', timereversal=.true., & + headrankonly=.false., mw=mw, mem=mem, verbosity=opts%verbosity) + if (mw%talk) write(*, *) '... generating harmonic dispersion' + call dr%generate(qp, fc, uc, mw=mw, mem=mem, verbosity=opts%verbosity) + + call free_energy_fourthorder(uc, fcf, qp, dr, opts%temperature, fe4, s4, cv4, opts%quantum, mw, mem) + thermo%fourphonon%F(1) = fe4 + thermo%fourphonon%S(1) = s4 + thermo%fourphonon%U(1) = (fe4 + opts%temperature * s4) + thermo%fourphonon%Cv(1) = cv4 end if + call tmr%tock('four-phonon') +end block latdyn4ph + +summary: block + !> Unit conversion factor + real(r8) :: f_unit, e_unit, s_unit, c_unit, p_unit + !> Buffer for the stress tensor + real(r8), dimension(3, 3) :: sigma + !> Some buffer to print the results + real(r8), dimension(4) :: buf, buf3, buf4 + !> The pressure + real(r8) :: pressure + !> To have a pretty logfile + character(len=1000) :: opfc, opff, opfs + !> Some integers + integer :: i, u + + f_unit = lo_Hartree_to_eV + e_unit = lo_Hartree_to_eV + s_unit = 1.0 / lo_kb_Hartree + c_unit = 1.0 / lo_kb_Hartree + ! p_unit = lo_pressure_HartreeBohr_to_GPa + + ! Get the stress tensor (harmonic + threephonon only) + ! sigma = (thermo%harmonic%stress(:, :, 1) + thermo%threephonon%stress(:, :, 1)) * p_unit + ! pressure = lo_trace(sigma) / 3.0_r8 + if (mw%talk) then - opf = '(1X,A23,1X,F20.7)' - ! Write on a file - u = open_file('out', 'outfile.anharmonic_free_energy') - fe2_1 = (cumulant(1, 3) + f_ph)*lo_Hartree_to_eV - fe2_2 = (cumulant(1, 3) + f_ph + pref*cumulant(2, 3))*lo_Hartree_to_eV - write (u, "(1X, A17, F8.2, 1X, A17)") '# Free energy at ', sim%temperature_thermostat, 'K, unit : eV/atom' - write (u, *) '# Lowest order (1st order cumulant, 2nd order cumulant)' - write (u, "(1X, 2(F25.10,' '))") fe2_1, fe2_2 - write (*, *) '' - write (*, *) 'Lowest order approximation to the free energy (eV/atom):' - write (*, *) 'Calculated as + F_phonon' - write (*, opf) 'F =', fe2_1 - write (*, opf) 'F_phonon =', f_ph*lo_Hartree_to_eV - write (*, opf) 'Second order cumulant =', cumulant(2, 3)*lo_Hartree_to_eV - write (*, opf) 'Third order cumulant =', cumulant(3, 3)*lo_Hartree_to_eV - if (opts%thirdorder .or. opts%fourthorder) then - fe3_1 = (cumulant(1, 4) + f_ph + ah3)*lo_Hartree_to_eV - fe3_2 = (cumulant(1, 4) + f_ph + ah3 + pref*cumulant(2, 4))*lo_Hartree_to_eV - write (u, *) '# Third order anharmonic corrections (1st order cumulant, 2nd order cumulant)' - write (u, "(1X, 2(F25.10,' '))") fe3_1, fe3_2 - write (*, *) '' - write (*, *) 'Free energy with third order anharmonic corrections (eV/atom):' - write (*, *) 'Calculated as + F_phonon + F_3' - write (*, opf) 'F =', fe3_1 - write (*, opf) 'F_phonon =', f_ph*lo_Hartree_to_eV - write (*, opf) 'F_3 =', ah3*lo_Hartree_to_eV - write (*, opf) 'Second order cumulant =', cumulant(2, 4)*lo_Hartree_to_eV - write (*, opf) 'Third order cumulant =', cumulant(3, 4)*lo_Hartree_to_eV + u = open_file('out', 'outfile.anharmonic_thermodynamics') + write(u, '(A2,A12,8X,E20.12)') '# ', 'Temperature:', opts%temperature + + opfc = '(4(1X,A24))' + opff = '(4(1X,F24.12))' + opfs = '(3(1X,F24.12))' + + ! Harmonic contribution + buf(1) = thermo%harmonic%F(1) * f_unit + buf(2) = thermo%harmonic%U(1) * e_unit + buf(3) = thermo%harmonic%S(1) * s_unit + buf(4) = thermo%harmonic%Cv(1) * c_unit + write(*, *) '' + write(*, *) 'SUMMARY OF RESULTS' + write(*, *) '' + write(*, *) 'Harmonic contribution' + write(*, opfc) 'Free energy [eV/at]', 'Internal energy [eV/at]', 'Entropy [kB]', 'Heat capacity [kB]' + write(*, opff) buf + write(u, *) '# Harmonic contribution' + write(u, opfc) '# Free energy [eV/at]', 'Internal energy [eV/at]', 'Entropy [kB]', 'Heat capacity [kB]' + write(u, opff) buf + + ! Fourth order (four-phonon) contribution + if (.not. opts%nofourthorder) then + buf4(1) = thermo%fourphonon%F(1) * f_unit + buf4(2) = thermo%fourphonon%U(1) * e_unit + buf4(3) = thermo%fourphonon%S(1) * s_unit + buf4(4) = thermo%fourphonon%Cv(1) * c_unit + write(*, *) '' + write(*, *) 'First Cumulant Contribution' + write(*, opfc) 'Free energy [eV/at]', 'Internal energy [eV/at]', 'Entropy [kB]', 'Heat capacity [kB]' + write(*, opff) buf4 + write(u, *) '# First Cumulant Contribution' + write(u, opfc) '# Free energy [eV/at]', 'Internal energy [eV/at]', 'Entropy [kB]', 'Heat capacity [kB]' + write(u, opff) buf4 end if - if (opts%fourthorder) then - fe4_1 = (cumulant(1, 5) + f_ph + ah3 + ah4)*lo_Hartree_to_eV - fe4_2 = (cumulant(1, 5) + f_ph + ah3 + ah4 + pref*cumulant(2, 5))*lo_Hartree_to_eV - write (u, *) '# Fourth order anharmonic corrections (1st order cumulant, 2nd order cumulant)' - write (u, "(1X, 2(F25.10,' '))") fe4_1, fe4_2 - write (*, *) '' - write (*, *) 'Free energy with fourth order anharmonic corrections (eV/atom):' - write (*, *) 'Calculated as + F_phonon + F_3 + F_4' - write (*, opf) 'F =', fe4_1 - write (*, opf) 'F_phonon =', f_ph*lo_Hartree_to_eV - write (*, opf) 'F_3 =', ah3*lo_Hartree_to_eV - write (*, opf) 'F_4 =', ah4*lo_Hartree_to_eV - write (*, opf) 'Second order cumulant =', cumulant(2, 5)*lo_Hartree_to_eV - write (*, opf) 'Third order cumulant =', cumulant(3, 5)*lo_Hartree_to_eV + + ! Third order (three-phonon) contribution + if (.not. opts%nothirdorder) then + buf3(1) = thermo%threephonon%F(1) * f_unit + buf3(2) = thermo%threephonon%U(1) * e_unit + buf3(3) = thermo%threephonon%S(1) * s_unit + buf3(4) = thermo%threephonon%Cv(1) * c_unit + write(*, *) '' + write(*, *) 'Second Cumulant Contribution' + write(*, opfc) 'Free energy [eV/at]', 'Internal energy [eV/at]', 'Entropy [kB]', 'Heat capacity [kB]' + write(*, opff) buf3 + write(u, *) '# Second Cumulant Contribution' + write(u, opfc) '# Free energy [eV/at]', 'Internal energy [eV/at]', 'Entropy [kB]', 'Heat capacity [kB]' + write(u, opff) buf3 end if - end if -end block getenergy + close(u) + end if -! Kill MPI -call mw%destroy() + call tmr%stop() + if (mw%talk) write(*, *) '' + call tmr%dump(mw, 'Timings:') +end block summary +! And we are done! +call mpi_barrier(mw%comm, mw%error) +call mpi_finalize(lo_status) end program diff --git a/src/anharmonic_free_energy/manual.md b/src/anharmonic_free_energy/manual.md index 5ba7e953..534d7d9e 100644 --- a/src/anharmonic_free_energy/manual.md +++ b/src/anharmonic_free_energy/manual.md @@ -1,5 +1,7 @@ -This code calculates the anharmonic Helmholtz free energy. It includes the contributions from baseline shifts, renormalized phonons and higher order terms. +This code calculates the anharmonic part of the Helmholtz free energy, internal energy, entropy and heat capacity. It includes the contributions from baseline shifts, renormalized phonons and higher order terms. This program must use force constants from sTDEP/SSCHA (self-consistent phonons). Force cosntants fit to MD/PIMD data are incompatible with this theory. + +Only the first and second-cumulant corrections are computed by this code. The constant corrections (i.e., $U_0$ and its derivatives) must be implemented elsewhere as it requires interfacing with a force-calculator like LAMMPS. Please refer to CITATION and a reference implementation [here](https://github.com/ejmeitz/CumulantAnalysis.jl). ### Longer summary @@ -38,7 +40,7 @@ $$ \end{equation} $$ -where $F_{\textrm{ph}}$ is the usual phonon free energy and $U_0$ the renormalized baseline free energy given by +where $F_{\textrm{ph}}$ is the phonon free energy and $U_0$ the renormalized baseline free energy. However, since the derivations of $\Delta F^{3\mathrm{ph}}$ and $\Delta F^{4\mathrm{ph}}$ assume self-consistent phonons the average is with respect to harmonic dynamics (i.e., $\langle \cdot \rangle_\mathrm{H}$). The expression is given by $$ \begin{equation} @@ -57,7 +59,7 @@ u_i^\alpha u_j^\beta u_k^\gamma - }} \Phi_{ijkl}^{\alpha\beta\gamma\delta} u_i^\alpha u_j^\beta u_k^\gamma u_l^\delta - \right\rangle + \right\rangle_\mathrm{H} \end{equation} $$ @@ -65,26 +67,8 @@ Here it is important to note that we have to subtract the long-ranged polar inte $$ \begin{equation}%\label{eq:deltaF3} - \Delta F^{3\textrm{ph}} = - -6 - \sum_{\lambda\lambda'\lambda''} - \left| - \Phi_{\lambda\lambda'\lambda''} - \right|^2 - % - \left( - %\Bigg{\{} - \frac{3n_{\lambda} n_{\lambda'} + 3n_{\lambda} + 1} - {(\omega_{\lambda}+\omega_{\lambda'}+\omega_{\lambda''})_p} - + - \frac{ 6n_{\lambda} n_{\lambda''} - 3 n_{\lambda} n_{\lambda'} + 3n_{\lambda''}} - {(\omega_{\lambda}+\omega_{\lambda'}-\omega_{\lambda''})_p} - \right) - %\Bigg{\}} - % - +9\Phi_{\lambda\bar{\lambda}\lambda''}\Phi_{\lambda'\bar{\lambda}'\bar{\lambda}''} - \frac{4 n_{\lambda}( n_{\lambda'}+1)+1} - {(\omega_{\lambda''})_p}\,, + \Delta F^{3\textrm{ph}} = -\frac{\hbar^2}{48N}\sum_{\substack{\bm k\bm k^\prime \bm k^{\prime\prime} \\ \lambda\lambda^\prime\lambda^{\prime\prime}}}\frac{\left|\Phi_{\lambda \lambda^\prime \lambda^{\prime\prime}} ^ {\bm k \bm k^\prime \bm k^{\prime\prime}}\right|^2}{\omega\omega^\prime\omega^{\prime\prime}} \left[\frac{(n+1)(n^\prime + n^{\prime\prime} + 1) + n^\prime n^{\prime\prime}}{\omega + \omega^\prime + \omega^{\prime\prime}} + + 3\frac{n^{\prime\prime}(n+n^\prime+1)-nn^\prime}{\omega + \omega^\prime - \omega^{\prime\prime}}\right] \end{equation} $$ @@ -93,8 +77,7 @@ and $$ \begin{equation}%\label{eq:deltaF4} \Delta F^{4\textrm{ph}} = - 3\sum_{\lambda\lambda'} - \Phi_{\lambda\bar{\lambda}\lambda'\bar{\lambda}'}(2n_{\lambda}+1)(2n_{\lambda'}+1) + \frac{\hbar^2}{8N}\sum_{\bm k\ \bm k^\prime \lambda\lambda^\prime}\frac{\Phi_{\lambda\lambda\lambda^\prime\lambda^\prime}^{\bm k,-\bm k,\bm k^\prime,-\bm k^\prime}}{\omega\omega^{\prime}}\left(n+\frac{1}{2}\right)\left(n^\prime + \frac{1}{2}\right) \end{equation} $$ diff --git a/src/anharmonic_free_energy/options.f90 b/src/anharmonic_free_energy/options.f90 index e7c1f3f8..0c1ed528 100644 --- a/src/anharmonic_free_energy/options.f90 +++ b/src/anharmonic_free_energy/options.f90 @@ -1,7 +1,6 @@ #include "precompilerdefinitions" module options -use konstanter, only: r8, lo_author, lo_version, lo_licence, lo_tiny, lo_status, lo_exitcode_baddim, lo_exitcode_param, & - lo_frequency_Hartree_to_THz, lo_frequency_Hartree_to_icm, lo_frequency_Hartree_to_meV +use konstanter, only: r8, lo_author, lo_version, lo_licence, lo_status, lo_exitcode_baddim use gottochblandat, only: lo_stop_gracefully use flap, only: command_line_interface implicit none @@ -9,13 +8,13 @@ module options public :: lo_opts type lo_opts - integer, dimension(3) :: qgrid + real(r8) :: temperature + integer, dimension(3) :: qgh, qg3ph, qg4ph integer :: integrationtype integer :: verbosity logical :: quantum = .false. - logical :: stochastic = .false. - logical :: thirdorder = .false. - logical :: fourthorder = .false. + logical :: nothirdorder = .false. + logical :: nofourthorder = .false. contains procedure :: parse end type @@ -38,26 +37,37 @@ subroutine parse(opts) version=lo_version, & license=lo_licence, & help='Usage: ', & - description='Calculates the anharmonic free energy.', & + description='Calculates the anharmonic free energy given sTDEP force constants.', & examples=["mpirun anharmonic_free_energy"], & epilog=new_line('a')//"...") ! Specify some options - cli_qpoint_grid + call cli%add(switch='--qpoint_harmonic', switch_ab='-qgh', & + help='Dimension of the q-grid for harmonic contributions', & + nargs='3', required=.false., act='store', def='25 25 25', error=lo_status) + if (lo_status .ne. 0) stop + call cli%add(switch='--qpoint_grid3ph', switch_ab='-qg3ph', & + help='Dimension of the q-grid for three phonon contribution', & + nargs='3', required=.false., act='store', def='20 20 20', error=lo_status) + if (lo_status .ne. 0) stop + call cli%add(switch='--qpoint_grid4ph', switch_ab='-qg4ph', & + help='Dimension of the q-grid for four phonon contribution', & + nargs='3', required=.false., act='store', def='20 20 20', error=lo_status) + if (lo_status .ne. 0) stop + call cli%add(switch='--temperature', & + help='The temperature at which the thermodynamic properties are computed', & + required=.false., act='store', def='300', error=lo_status) + if (lo_status .ne. 0) stop call cli%add(switch='--quantum', & help='Use Bose-Einstein occupations to compute the free energy', & required=.false., act='store_true', def='.false.', error=lo_status) if (lo_status .ne. 0) stop - call cli%add(switch='--stochastic', & - help='Add second order cumulant contribution to the free energy with a minus sign for self-consistent sampling', & - required=.false., act='store_true', def='.false.', error=lo_status) - if (lo_status .ne. 0) stop - call cli%add(switch='--thirdorder', & - help='Compute third order anharmonic correction to the free energy', & + call cli%add(switch='--nothirdorder', & + help='Do NOT compute third order anharmonic correction to the free energy', & required=.false., act='store_true', def='.false.', error=lo_status) if (lo_status .ne. 0) stop - call cli%add(switch='--fourthorder', & - help='Compute fourth order anharmonic correction to the free energy', & + call cli%add(switch='--nofourthorder', & + help='Do NOT compute fourth order anharmonic correction to the free energy', & required=.false., act='store_true', def='.false.', error=lo_status) if (lo_status .ne. 0) stop cli_manpage @@ -79,17 +89,24 @@ subroutine parse(opts) call cli%get(switch='--verbose', val=dumlog, error=lo_status); errctr = errctr + lo_status; if (dumlog) opts%verbosity = 2 ! get real options - call cli%get(switch='--qpoint_grid', val=opts%qgrid, error=lo_status); errctr = errctr + lo_status + call cli%get(switch='--temperature', val=opts%temperature, error=lo_status); errctr = errctr + lo_status call cli%get(switch='--quantum', val=opts%quantum, error=lo_status); errctr = errctr + lo_status - call cli%get(switch='--stochastic', val=opts%stochastic, error=lo_status); errctr = errctr + lo_status - call cli%get(switch='--thirdorder', val=opts%thirdorder, error=lo_status); errctr = errctr + lo_status - call cli%get(switch='--fourthorder', val=opts%fourthorder, error=lo_status); errctr = errctr + lo_status - - ! If we have fourthorder we should also have thirdorder - if (opts%fourthorder) opts%thirdorder = .true. + call cli%get(switch='--nothirdorder', val=opts%nothirdorder, error=lo_status); errctr = errctr + lo_status + call cli%get(switch='--nofourthorder', val=opts%nofourthorder, error=lo_status); errctr = errctr + lo_status + call cli%get(switch='--qpoint_harmonic', val=opts%qgh, error=lo_status); errctr = errctr + lo_status + call cli%get(switch='--qpoint_grid3ph', val=opts%qg3ph, error=lo_status); errctr = errctr + lo_status + call cli%get(switch='--qpoint_grid4ph', val=opts%qg4ph, error=lo_status); errctr = errctr + lo_status if (errctr .ne. 0) call lo_stop_gracefully(['Failed parsing the command line options'], lo_exitcode_baddim) + if (maxval(opts%qg3ph) .gt. 0 .and. opts%nothirdorder) then + write(*, *) 'WARNING: You turned off thirdorder but still specified a three-phonon q-grid.' + end if + + if (maxval(opts%qg4ph) .gt. 0 .and. opts%nofourthorder) then + write(*, *) 'WARNING: You turned off fourthorder but still specified a four-phonon q-grid.' + end if + end subroutine end module diff --git a/src/anharmonic_free_energy/thirdorder.f90 b/src/anharmonic_free_energy/thirdorder.f90 new file mode 100644 index 00000000..9a9e8bfa --- /dev/null +++ b/src/anharmonic_free_energy/thirdorder.f90 @@ -0,0 +1,389 @@ +module thirdorder +!! Compute the third order contribution to the anharmonic free energy +use konstanter, only: r8, lo_freqtol, lo_twopi, lo_imag, lo_kb_Hartree, lo_exitcode_param +use gottochblandat, only: walltime, lo_trueNtimes, lo_progressbar_init, lo_progressbar, lo_planck, & + lo_planck_deriv, lo_planck_secondderiv, lo_invert_real_matrix, & + lo_harmonic_oscillator_cv, lo_harmonic_oscillator_internal_energy +use mpi_wrappers, only: lo_mpi_helper, lo_stop_gracefully +use lo_memtracker, only: lo_mem_helper +use type_qpointmesh, only: lo_qpoint_mesh, lo_fft_mesh +use type_crystalstructure, only: lo_crystalstructure +use type_forceconstant_secondorder, only: lo_forceconstant_secondorder +use type_forceconstant_thirdorder, only: lo_forceconstant_thirdorder +use type_phonon_dispersions, only: lo_phonon_dispersions +use type_symmetryoperation, only: lo_operate_on_secondorder_tensor +use lo_timetracker, only: lo_timer +use lo_fftgrid_helper, only: fft_third_grid_index + +use lo_thermodynamic_helpers, only: lo_full_to_voigt + +implicit none +private + +public :: elastic_thirdorder +public :: free_energy_thirdorder + +contains +subroutine elastic_thirdorder(uc, fc, fct, qp, dr, temperature, p3ph, alpha, quantum, mw, mem) + !> crystal structure + type(lo_crystalstructure), intent(in) :: uc + !> second order force constants + type(lo_forceconstant_secondorder), intent(inout) :: fc + !> third order force constant + type(lo_forceconstant_thirdorder), intent(in) :: fct + !> q-point mesh + class(lo_qpoint_mesh), intent(in) :: qp + !> dispersions + type(lo_phonon_dispersions), intent(in) :: dr + !> temperature + real(r8), intent(in) :: temperature + !> free energies and heat capacity + real(r8), dimension(3, 3), intent(out) :: p3ph, alpha + !> what to compute + logical, intent(in) :: quantum + !> mpi helper + type(lo_mpi_helper), intent(inout) :: mw + !> memory tracker + type(lo_mem_helper), intent(inout) :: mem + + !> The eigenvector for the current mode + complex(r8), dimension(:), allocatable :: egv + !> Complex coefficients for gruneisen + complex(r8), dimension(3, 3) :: c0 + !> stiffness and compliance tensors, in voigt notation + real(r8), dimension(6, 6) :: cij, sij + !> Buffers for Gruneisen and thermal expansion, with full anisotropy + real(r8), dimension(3, 3) :: grun, bufalpha, grunbuf + !> q-points and lattice distances + real(r8), dimension(3) :: qv, rv2, rv3 + !> Phase factor for Fourier transform and product of eigenvectors + complex(r8) :: expiqr, evprod + !> Harmonic stuffs + real(r8) :: om, iqr, invsqrtmass, u0, cv0 + !> Integers for do loops + integer :: q1, b1, a1, t, a2, a3, i, j, k, l, ivoigt, jvoigt, ctr, ifull + + ! We start by allocating space for the eigenvector + call mem%allocate(egv, dr%n_mode, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + + ! Set everything to zero + p3ph = 0.0_r8 + bufalpha = 0.0_r8 + + ! And here we go + ctr = 0 + do q1=1, qp%n_irr_point + qv = qp%ip(q1)%r * lo_twopi + do b1=1, dr%n_mode + ctr = ctr + 1 + if (mod(ctr, mw%n) .ne. mw%r) cycle + ! We start by computing the mode Gruneisen parameter, with full anisotropy + om = dr%iq(q1)%omega(b1) + if (om .lt. lo_freqtol) cycle + c0 = 0.0_r8 + egv = dr%iq(q1)%egv(:, b1) + do a1=1, fct%na + do t=1, fct%atom(a1)%n + a2 = fct%atom(a1)%triplet(t)%i2 + a3 = fct%atom(a1)%triplet(t)%i3 + rv2 = fct%atom(a1)%triplet(t)%lv2 + rv3 = fct%atom(a1)%triplet(t)%rv3 + invsqrtmass = uc%invsqrtmass(a1) * uc%invsqrtmass(a2) + iqr = -dot_product(qv, rv2) + expiqr = cmplx(cos(iqr), sin(iqr), r8) + do i=1, 3 + do j=1, 3 + evprod = conjg(egv((a1-1) * 3 + i)) * egv((a2-1) * 3 + j) * expiqr + do k=1, 3 + do l=1, 3 + c0(k, l) = c0(k, l) + fct%atom(a1)%triplet(t)%m(i, j, k) * evprod * rv3(l) * invsqrtmass + end do + end do + end do + end do + end do + end do + grun = -real(c0, r8) / (6.0_r8 * om**2) + + ! Here we sum over all symmetry equivalent q-point, taking into account the symop + grunbuf = 0.0_r8 + do ifull=1, qp%ip(q1)%n_full_point + grunbuf = grunbuf + lo_operate_on_secondorder_tensor(uc%sym%op(ifull), grun) + end do + grun = grunbuf + + ! Now we can accumulate things using the Gruneisen parameter + if (quantum) then + u0 = lo_harmonic_oscillator_internal_energy(temperature, om) + cv0 = lo_harmonic_oscillator_cv(temperature, om) + else + u0 = lo_kb_Hartree * temperature + cv0 = lo_kb_Hartree + end if + + ! And we accumulate + p3ph(:, :) = p3ph(:, :) - grun(:, :) * u0 / uc%volume / qp%n_full_point + bufalpha(:, :) = bufalpha(:, :) + cv0 * grun(:, :) / qp%n_full_point + end do + end do + ! Reduce the calculation + call mw%allreduce('sum', p3ph) + call mw%allreduce('sum', bufalpha) + + ! We need the compliance tensor to get the thermal expansion + call fc%get_elastic_constants(uc, mw, -1) + cij = fc%elastic_constants_voigt + fc%elastic_constants_voigt_longrange + call lo_invert_real_matrix(cij, sij) + + ! And we just have to add the compliance tensor part to get the thermal expansion + alpha = 0.0_r8 + do i=1, 3 + do j=1, 3 + do k=1, 3 + do l=1, 3 + ivoigt = lo_full_to_voigt(i, j) + jvoigt = lo_full_to_voigt(k, l) + + ! That's simply the formula + alpha(i, j) = alpha(i, j) + sij(ivoigt, jvoigt) * bufalpha(k, l) / uc%volume + end do + end do + end do + end do + call mem%deallocate(egv, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) +end subroutine + +!> Calculate the third order free energy +subroutine free_energy_thirdorder(uc, fct, qp, dr, temperature, fe3, s3, cv3, quantum, mw, mem) + !> crystal structure + type(lo_crystalstructure), intent(in) :: uc + !> third order force constant + type(lo_forceconstant_thirdorder), intent(in) :: fct + !> q-point mesh + class(lo_qpoint_mesh), intent(in) :: qp + !> dispersions + type(lo_phonon_dispersions), intent(in) :: dr + !> temperature + real(r8) :: temperature + !> free energies and heat capacity + real(r8), intent(out) :: fe3, s3, cv3 + !> what to compute + logical, intent(in) :: quantum + !> mpi helper + type(lo_mpi_helper), intent(inout) :: mw + !> memory tracker + type(lo_mem_helper), intent(inout) :: mem + + !> For the smearing parameters + real(r8), dimension(:, :), allocatable :: sigsq + !> Frequency scaled eigenvectors + complex(r8), dimension(:), allocatable :: egv1, egv2, egv3 + !> Helper for Fourier transform of psi3 + complex(r8), dimension(:), allocatable :: ptf, evp1, evp2 + !> Frequencies, bose-einstein occupation and scattering strength and some other buffer + real(r8) :: sigma, om1, om2, om3, n2, n3, psisq, f0, f1, plf0, plf1, perm, f2, n1, pref, t0, prefactor + !> + real(r8) :: sig1, sig2, sig3, dn1, dn2, dn3, ddn1, ddn2, ddn3, df1, df2, ddf1, ddf2, df0, ddf0 + !> The complex threephonon matrix element + complex(r8) :: c0 + !> Integers for do loops and counting + integer :: qi, q1, q2, q3, q2p, q3p, b1, b2, b3, i, ctr + !> The dimension of the q-grid + integer, dimension(3) :: dims + + ! We start by allocating everything + call mem%allocate(ptf, dr%n_mode**3, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%allocate(evp1, dr%n_mode**2, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%allocate(evp2, dr%n_mode**3, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%allocate(egv1, dr%n_mode, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%allocate(egv2, dr%n_mode, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%allocate(egv3, dr%n_mode, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%allocate(sigsq, [qp%n_irr_point, dr%n_mode], persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + + t0 = walltime() + + select type (qp) + class is (lo_fft_mesh) + dims = qp%griddensity + class default + call lo_stop_gracefully(['This routine only works with FFT meshes'], lo_exitcode_param, __FILE__, __LINE__) + end select + + fe3 = 0.0_r8 + s3 = 0.0_r8 + cv3 = 0.0_r8 + + ! First we compute the broadening parameter for each modes + sigsq = 0.0_r8 + do q1=1, qp%n_irr_point + do b1=1, dr%n_mode + sigsq(q1, b1) = qp%smearingparameter(dr%iq(q1)%vel(:, b1), dr%default_smearing(b1), 1.0_r8)**2 + end do + end do + + if (mw%talk) call lo_progressbar_init() + do q1=1, qp%n_irr_point + do q2=1, qp%n_full_point + ctr = ctr + 1 + if (mod(ctr, mw%n) .ne. mw%r) cycle + q3 = fft_third_grid_index(qp%ip(q1)%full_index, q2, dims) + + + prefactor = qp%ip(q1)%integration_weight*qp%ap(q2)%integration_weight/uc%na + ! pre-transform the matrix element + call pretransform_phi3(fct, qp%ap(q2)%r, qp%ap(q3)%r, ptf) + + do b1=1, dr%n_mode + ! Get first phonon + om1 = dr%iq(q1)%omega(b1) + if (om1 .lt. lo_freqtol) cycle + n1 = lo_planck(temperature, om1) + dn1 = lo_planck_deriv(temperature, om1) + ddn1 = lo_planck_secondderiv(temperature, om1) + egv1 = dr%iq(q1)%egv(:, b1)/sqrt(om1) + do b2=1, dr%n_mode + ! Get second phonon + om2 = dr%aq(q2)%omega(b2) + if (om2 .lt. lo_freqtol) cycle + n2 = lo_planck(temperature, om2) + dn2 = lo_planck_deriv(temperature, om2) + ddn2 = lo_planck_secondderiv(temperature, om2) + egv2 = dr%aq(q2)%egv(:, b2)/sqrt(om2) + + ! Multiply first and second phonon + evp1 = 0.0_r8 + call zgeru(dr%n_mode, dr%n_mode, (1.0_r8, 0.0_r8), egv2, 1, egv1, 1, evp1, dr%n_mode) + do b3=1, dr%n_mode + ! Get third phonon + om3 = dr%aq(q3)%omega(b3) + if (om3 .lt. lo_freqtol) cycle + n3 = lo_planck(temperature, om3) + dn3 = lo_planck_deriv(temperature, om3) + ddn3 = lo_planck_secondderiv(temperature, om3) + egv3 = dr%aq(q3)%egv(:, b3)/sqrt(om3) + + ! Project on third phonon + evp2 = 0.0_r8 + call zgeru(dr%n_mode, dr%n_mode**2, (1.0_r8, 0.0_r8), egv3, 1, evp1, 1, evp2, dr%n_mode) + evp2 = conjg(evp2) + + ! Compute the scattering matrix element + c0 = dot_product(evp2, ptf) + psisq = real(conjg(c0)*c0, r8) * prefactor + + if (quantum) then + ! Get a smearing parameter + sig1 = sigsq(q1, b1) + sig2 = sigsq(qp%ap(q2)%irreducible_index, b2) + sig3 = sigsq(qp%ap(q3)%irreducible_index, b3) + sigma = sqrt(sig1 + sig2 + sig3) + + ! This are the formula to get the free energy + f1 = (n1 + 1.0_r8)*(n2 + n3 + 1.0_r8) + n2*n3 + f2 = n3*(n1 + n2 + 1.0_r8) - n1*n2 + ! Here is for the entropy + df1 = dn1 * (n2 + n3 + 1.0_r8) + (n1 + 1.0_r8) * (dn2 + dn3) + (dn2 * n3) + (n2 * dn3) + df2 = dn3 * (n1 + n2 + 1.0_r8) + (dn1 * (n3 - n2)) + (dn2 * (n3 - n1)) + ! And the heat capacity + ddf1 = ddn1 * (n2 + n3 + 1.0_r8) + 2.0_r8 * dn1 * (dn2 + dn3) + (n1 + 1.0_r8) * (ddn2 + ddn3) + & + ddn2 * n3 + n2 * ddn3 + 2.0_r8 * dn2 * dn3 + ddf2 = (ddn3 * (n1 + n2 + 1.0_r8)) + (dn3 * (dn1 + dn2)) + & + (ddn1 * (n3 - n2)) + (dn1 * (dn3 - dn2)) + & + (ddn2 * (n3 - n1)) + (dn2 * (dn3 - dn1)) + + ! Compute the principal values + f1 = f1*real(1.0_r8/(om1 + om2 + om3 + lo_imag*sigma), r8) + df1 = df1*real(1.0_r8/(om1 + om2 + om3 + lo_imag*sigma), r8) + ddf1 = ddf1*real(1.0_r8/(om1 + om2 + om3 + lo_imag*sigma), r8) + f2 = 3.0_r8*f2*real(1.0/(om1 + om2 - om3 + lo_imag*sigma), r8) + df2 = 3.0_r8 * df2 * real(1.0/(om1 + om2 - om3 + lo_imag*sigma), r8) + ddf2 = 3.0_r8 * ddf2 * real(1.0/(om1 + om2 - om3 + lo_imag*sigma), r8) + + ! Get everything together + f0 = (f1 + f2) / 48.0_r8 + df0 = (df1 + df2) / 48.0_r8 + ddf0 = (ddf1 + ddf2) * temperature / 48.0_r8 + else + ! It's much simpler in the classical case + ! Free energy + f0 = (lo_kb_Hartree*temperature)**2 / (om1*om2*om3) / 12.0_r8 + ! Entropy + df0 = lo_kb_Hartree**2 * temperature / (om1*om2*om3) / 6.0_r8 + ! Heat capacity + ddf0 = lo_kb_Hartree**2 * temperature / (om1*om2*om3) / 6.0_r8 + end if + ! And accumulate + fe3 = fe3 - f0 * psisq + s3 = s3 + df0 * psisq + cv3 = cv3 + ddf0 * psisq + end do + end do + end do + end do + if (mw%talk .and. lo_trueNtimes(q1, 127, qp%n_irr_point)) then + call lo_progressbar(' ... third order', q1, qp%n_irr_point, walltime() - t0) + end if + end do + if (mw%talk) then + call lo_progressbar(' ... third order', qp%n_irr_point, qp%n_irr_point, walltime() - t0) + end if + ! Reduce on all ranks + call mw%allreduce('sum', fe3) + call mw%allreduce('sum', s3) + call mw%allreduce('sum', cv3) + + ! And we can deallocate everything + call mem%deallocate(ptf, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%deallocate(evp1, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%deallocate(evp2, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%deallocate(egv1, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%deallocate(egv2, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%deallocate(egv3, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) + call mem%deallocate(sigsq, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) +end subroutine + +!> Get the Fourier transform of the third order matrix element +subroutine pretransform_phi3(fct, q2, q3, ptf) + !> third order forceconstant + type(lo_forceconstant_thirdorder), intent(in) :: fct + !> q-vectors + real(r8), dimension(3), intent(in) :: q2, q3 + !> flattened, pretransformed matrix element + complex(r8), dimension(:), intent(out) :: ptf + + integer :: i, j, k, l + + complex(r8) :: expiqr + real(r8), dimension(3) :: rv2, rv3 + real(r8) :: iqr + integer :: a1, a2, a3, ia, ib, ic, t, nb + + nb = fct%na*3 + ptf = 0.0_r8 + do a1 = 1, fct%na + do t = 1, fct%atom(a1)%n + a2 = fct%atom(a1)%triplet(t)%i2 + a3 = fct%atom(a1)%triplet(t)%i3 + + rv2 = fct%atom(a1)%triplet(t)%lv2 + rv3 = fct%atom(a1)%triplet(t)%lv3 + + iqr = dot_product(q2, rv2) + dot_product(q3, rv3) + iqr = -iqr*lo_twopi + expiqr = cmplx(cos(iqr), sin(iqr), r8) + do i = 1, 3 + do j = 1, 3 + do k = 1, 3 + ia = (a1 - 1)*3 + i + ib = (a2 - 1)*3 + j + ic = (a3 - 1)*3 + k + ! Now for the grand flattening scheme, consistent with the zgeru operations above. + l = (ia - 1)*nb*nb + (ib - 1)*nb + ic + ptf(l) = ptf(l) + fct%atom(a1)%triplet(t)%mwm(i, j, k)*expiqr + end do + end do + end do + end do + end do +end subroutine +end module diff --git a/src/libolle/gottochblandat.f90 b/src/libolle/gottochblandat.f90 index ce75b0da..dc834127 100644 --- a/src/libolle/gottochblandat.f90 +++ b/src/libolle/gottochblandat.f90 @@ -73,6 +73,7 @@ module gottochblandat public :: lo_harmonic_oscillator_entropy public :: lo_harmonic_oscillator_free_energy public :: lo_harmonic_oscillator_internal_energy +public :: lo_classical_harmonic_oscillator_entropy public :: lo_index_in_periodic_array public :: lo_invert3x3matrix public :: lo_sqrt3x3matrix @@ -678,6 +679,11 @@ module elemental function lo_harmonic_oscillator_cv(temp,omega) result(cv) real(flyt), intent(in) :: omega real(flyt) :: cv end function + module elemental function lo_classical_harmonic_oscillator_entropy(temp,omega) result(s) + real(flyt), intent(in) :: temp + real(flyt), intent(in) :: omega + real(flyt) :: s + end function module subroutine lo_untangle_one_tetrahedron(corner,energy,groupvelocity,degentol,permutation,success,error_interp_energy,error_interp_gradient) real(r8), dimension(3,4), intent(in) :: corner real(r8), dimension(:,:), intent(in) :: energy diff --git a/src/libolle/gottochblandat_physics.f90 b/src/libolle/gottochblandat_physics.f90 index a5801e64..f9676c08 100644 --- a/src/libolle/gottochblandat_physics.f90 +++ b/src/libolle/gottochblandat_physics.f90 @@ -327,6 +327,27 @@ module elemental function lo_harmonic_oscillator_entropy(temp,omega) result(s) endif end function +module elemental function lo_classical_harmonic_oscillator_entropy(temp, omega) result(s) + !> Temperature in K + real(flyt), intent(in) :: temp + !> Angular frequency in hartree + real(flyt), intent(in) :: omega + !> The entropy in Hartreee/K + real(flyt) :: s + + if ( omega .lt. lo_freqtol ) then + s=0.0_flyt + return + endif + + if ( temp .lt. lo_temperaturetol ) then + s=0.0_flyt + return + endif + + s=lo_kb_Hartree*(1.0_r8 - log(omega/lo_kb_Hartree/temp)) +end function + !> Heat capacity (Cv) for a single harmonic oscillator in eV/K module elemental function lo_harmonic_oscillator_cv(temp,omega) result(cv) !> Temperature in K diff --git a/src/libolle/type_phonon_dispersions.f90 b/src/libolle/type_phonon_dispersions.f90 index e9877bc0..d22d99c8 100644 --- a/src/libolle/type_phonon_dispersions.f90 +++ b/src/libolle/type_phonon_dispersions.f90 @@ -9,10 +9,10 @@ module type_phonon_dispersions lo_Hartree_to_Joule, lo_exitcode_physical, lo_imag, lo_time_s_to_au use gottochblandat, only: open_file, walltime, tochar, lo_trueNtimes, lo_classical_harmonic_oscillator_free_energy, & lo_harmonic_oscillator_cv, lo_harmonic_oscillator_entropy, lo_harmonic_oscillator_free_energy, & - lo_planck, lo_sqnorm, lo_progressbar_init, lo_progressbar, qsort, lo_outerproduct, lo_chop, & - lo_symmetric_eigensystem_3x3matrix, lo_flattentensor, lo_unflatten_2tensor, & - lo_linear_least_squares, lo_nullspace_coefficient_matrix, lo_identitymatrix, & - lo_real_pseudoinverse, lo_determ + lo_classical_harmonic_oscillator_entropy, lo_planck, lo_sqnorm, lo_progressbar_init, & + lo_progressbar, qsort, lo_outerproduct, lo_chop, lo_symmetric_eigensystem_3x3matrix, & + lo_flattentensor, lo_unflatten_2tensor, lo_linear_least_squares, lo_nullspace_coefficient_matrix, & + lo_identitymatrix, lo_real_pseudoinverse, lo_determ use mpi_wrappers, only: lo_mpi_helper, lo_stop_gracefully use lo_memtracker, only: lo_mem_helper use type_blas_lapack_wrappers, only: lo_gemm, lo_gemv @@ -138,6 +138,8 @@ module type_phonon_dispersions procedure :: phonon_angular_momentum_matrix !> thermal displacement covariance matrix procedure :: thermal_displacement_matrix + !> kinetic contribution to the stress tensor + procedure :: phonon_kinetic_stress !> store the full grid in a hdf file procedure :: write_to_hdf5 !> store the irreducible grid in a hdf5 file @@ -864,6 +866,58 @@ pure function phonon_entropy(dr, temperature, modenum, sitenum) result(s) s = s/dr%n_full_qpoint/(dr%n_mode/3) end function +!> calculate the phonon entropy as a direct sum +pure function phonon_entropy_classical(dr, temperature, modenum, sitenum) result(s) + !> the phonon dispersions + class(lo_phonon_dispersions), intent(in) :: dr + !> the temperature + real(r8), intent(in) :: temperature + !> the entropy in eV/K/atom (entropy for the modenum-th mode if modenum is specified) + real(r8) :: s + !> calculate vibrational entropy for a specific mode + integer, intent(in), optional :: modenum + !> project entropy onto a specific site + integer, intent(in), optional :: sitenum + + complex(r8), dimension(3) :: cv0 + real(r8) :: w + integer :: i, j + + ! Calculate the entropy of only one mode if modenum is specified + if (present(modenum)) then + j = modenum + s = 0.0_r8 + do i = 1, dr%n_full_qpoint + s = s + lo_classical_harmonic_oscillator_entropy(temperature, dr%aq(i)%omega(j)) + end do + s = s/dr%n_full_qpoint/(dr%n_mode/3) + return + end if + + ! If modenum or sitenum was not specified, calculate the total entropy + if (present(sitenum)) then + s = 0.0_r8 + do i = 1, dr%n_full_qpoint + do j = 1, dr%n_mode + cv0 = dr%aq(i)%egv((sitenum - 1)*3 + 1:sitenum*3, j) + w = abs(dot_product(cv0, cv0)) + s = s + w*lo_classical_harmonic_oscillator_entropy(temperature, dr%aq(i)%omega(j)) + end do + end do + s = s/dr%n_full_qpoint/(dr%n_mode/3) + return + end if + + ! If modenum or sitenum was not specified, calculate the total entropy + s = 0.0_r8 + do i = 1, dr%n_full_qpoint + do j = 1, dr%n_mode + s = s + lo_classical_harmonic_oscillator_entropy(temperature, dr%aq(i)%omega(j)) + end do + end do + s = s/dr%n_full_qpoint/(dr%n_mode/3) +end function + !> calculate phonon angular momentum matrix subroutine phonon_angular_momentum_matrix(dr, qp, uc, temperature, alpha, mw) !> dispersion relations @@ -1079,6 +1133,42 @@ subroutine thermal_displacement_matrix(dr, qp, uc, temperature, sigma, mw, mem) call mem%deallocate(vX, persistent=.false., scalable=.false., file=__FILE__, line=__LINE__) end subroutine +!> Calculate the kinetic contribution to the stress tensor +subroutine phonon_kinetic_stress(dr, qp, uc, temperature, kinsigma) + !> dispersion relations + class(lo_phonon_dispersions), intent(in) :: dr + !> qpoint mesh + class(lo_qpoint_mesh), intent(in) :: qp + !> crystal structure + type(lo_crystalstructure), intent(in) :: uc + !> temperature + real(r8), intent(in) :: temperature + !> displacement covariance matrix + real(r8), dimension(3, 3), intent(out) :: kinsigma + + !> The eigenvector for a given mode + complex(r8), dimension(3) :: egv + !> Some buffers + real(r8) :: pref, om, f0 + !> Integers for do loop + integer :: aq, im, a + + kinsigma = 0.0_r8 + pref = 1.0_r8 / uc%volume / qp%n_full_point + do aq=1, qp%n_full_point + do im=1, dr%n_mode + om = dr%aq(aq)%omega(im) + if (om .lt. lo_freqtol) cycle + f0 = om * (lo_planck(temperature, om) + 0.5_r8) * pref + do a=1, uc%na + egv = dr%aq(aq)%egv((a - 1)*3 + 1:a*3, im) + kinsigma(:, :) = kinsigma(:, :) + real(lo_outerproduct(egv, egv)) * f0 + end do + end do + end do + kinsigma(:, :) = lo_chop(kinsigma(:, :), 1e-12_r8) +end subroutine + !> Calculate all the harmonic things for a q-point subroutine harmonic_things_for_single_point(ompoint, fc, p, mem, qpoint, qvec, qdirection) !> point in the dispersions diff --git a/tests/anharmonic_free_energy/Argon_80K_classical/infile.forceconstant b/tests/anharmonic_free_energy/Argon_80K_classical/infile.forceconstant new file mode 100644 index 00000000..e6b58490 --- /dev/null +++ b/tests/anharmonic_free_energy/Argon_80K_classical/infile.forceconstant @@ -0,0 +1,399 @@ + 1 How many atoms per unit cell + 8.295919213738646 Realspace cutoff (A) + 79 How many neighbours does atom 1 have + 1 In the unit cell, what is the index of neighbour 1 of atom 1 + 0.0000000000000000 0.0000000000000000 0.0000000000000000 + 0.44889178211100261 0.0000000000000000 0.0000000000000000 + 0.0000000000000000 0.44889178211100256 0.0000000000000000 + 0.0000000000000000 0.0000000000000000 0.44889178211100261 + 1 In the unit cell, what is the index of neighbour 2 of atom 1 + -1.0000000000000000 1.0000000000000000 0.0000000000000000 + -5.9723718853086610E-002 0.0000000000000000 6.3253514816645873E-002 + 0.0000000000000000 3.8307737422309911E-003 0.0000000000000000 + 6.3253514816645873E-002 0.0000000000000000 -5.9723718853086610E-002 + 1 In the unit cell, what is the index of neighbour 3 of atom 1 + 1.0000000000000000 -1.0000000000000000 0.0000000000000000 + -5.9723718853086610E-002 0.0000000000000000 6.3253514816645873E-002 + 0.0000000000000000 3.8307737422309911E-003 0.0000000000000000 + 6.3253514816645873E-002 0.0000000000000000 -5.9723718853086610E-002 + 1 In the unit cell, what is the index of neighbour 4 of atom 1 + 0.0000000000000000 0.0000000000000000 1.0000000000000000 + -5.9723718853086610E-002 0.0000000000000000 -6.3253514816645873E-002 + 0.0000000000000000 3.8307737422309911E-003 0.0000000000000000 + -6.3253514816645873E-002 0.0000000000000000 -5.9723718853086610E-002 + 1 In the unit cell, what is the index of neighbour 5 of atom 1 + -1.0000000000000000 0.0000000000000000 1.0000000000000000 + 3.8307737422309911E-003 0.0000000000000000 0.0000000000000000 + 0.0000000000000000 -5.9723718853086610E-002 6.3253514816645873E-002 + 0.0000000000000000 6.3253514816645873E-002 -5.9723718853086610E-002 + 1 In the unit cell, what is the index of neighbour 6 of atom 1 + -1.0000000000000000 0.0000000000000000 0.0000000000000000 + -5.9723718853086610E-002 -6.3253514816645873E-002 0.0000000000000000 + -6.3253514816645873E-002 -5.9723718853086610E-002 0.0000000000000000 + 0.0000000000000000 0.0000000000000000 3.8307737422309911E-003 + 1 In the unit cell, what is the index of neighbour 7 of atom 1 + 0.0000000000000000 1.0000000000000000 -1.0000000000000000 + -5.9723718853086610E-002 6.3253514816645873E-002 0.0000000000000000 + 6.3253514816645873E-002 -5.9723718853086610E-002 0.0000000000000000 + 0.0000000000000000 0.0000000000000000 3.8307737422309911E-003 + 1 In the unit cell, what is the index of neighbour 8 of atom 1 + 0.0000000000000000 1.0000000000000000 0.0000000000000000 + 3.8307737422309911E-003 0.0000000000000000 0.0000000000000000 + 0.0000000000000000 -5.9723718853086610E-002 -6.3253514816645873E-002 + 0.0000000000000000 -6.3253514816645873E-002 -5.9723718853086610E-002 + 1 In the unit cell, what is the index of neighbour 9 of atom 1 + 0.0000000000000000 -1.0000000000000000 0.0000000000000000 + 3.8307737422309911E-003 0.0000000000000000 0.0000000000000000 + 0.0000000000000000 -5.9723718853086610E-002 -6.3253514816645873E-002 + 0.0000000000000000 -6.3253514816645873E-002 -5.9723718853086610E-002 + 1 In the unit cell, what is the index of neighbour 10 of atom 1 + 0.0000000000000000 -1.0000000000000000 1.0000000000000000 + -5.9723718853086610E-002 6.3253514816645873E-002 0.0000000000000000 + 6.3253514816645873E-002 -5.9723718853086610E-002 0.0000000000000000 + 0.0000000000000000 0.0000000000000000 3.8307737422309911E-003 + 1 In the unit cell, what is the index of neighbour 11 of atom 1 + 1.0000000000000000 0.0000000000000000 0.0000000000000000 + -5.9723718853086610E-002 -6.3253514816645873E-002 0.0000000000000000 + -6.3253514816645873E-002 -5.9723718853086610E-002 0.0000000000000000 + 0.0000000000000000 0.0000000000000000 3.8307737422309911E-003 + 1 In the unit cell, what is the index of neighbour 12 of atom 1 + 1.0000000000000000 0.0000000000000000 -1.0000000000000000 + 3.8307737422309911E-003 0.0000000000000000 0.0000000000000000 + 0.0000000000000000 -5.9723718853086610E-002 6.3253514816645873E-002 + 0.0000000000000000 6.3253514816645873E-002 -5.9723718853086610E-002 + 1 In the unit cell, what is the index of neighbour 13 of atom 1 + 0.0000000000000000 0.0000000000000000 -1.0000000000000000 + -5.9723718853086610E-002 0.0000000000000000 -6.3253514816645873E-002 + 0.0000000000000000 3.8307737422309911E-003 0.0000000000000000 + -6.3253514816645873E-002 0.0000000000000000 -5.9723718853086610E-002 + 1 In the unit cell, what is the index of neighbour 14 of atom 1 + -1.0000000000000000 1.0000000000000000 -1.0000000000000000 + 3.8237713166163131E-003 0.0000000000000000 0.0000000000000000 + 0.0000000000000000 -2.9663166618997986E-004 0.0000000000000000 + 0.0000000000000000 0.0000000000000000 -2.9663166618997986E-004 + 1 In the unit cell, what is the index of neighbour 15 of atom 1 + -1.0000000000000000 1.0000000000000000 1.0000000000000000 + -2.9663166618997986E-004 0.0000000000000000 0.0000000000000000 + 0.0000000000000000 -2.9663166618997986E-004 0.0000000000000000 + 0.0000000000000000 0.0000000000000000 3.8237713166163131E-003 + 1 In the unit cell, what is the index of neighbour 16 of atom 1 + -1.0000000000000000 -1.0000000000000000 1.0000000000000000 + -2.9663166618997986E-004 0.0000000000000000 0.0000000000000000 + 0.0000000000000000 3.8237713166163131E-003 0.0000000000000000 + 0.0000000000000000 0.0000000000000000 -2.9663166618997986E-004 + 1 In the unit cell, what is the index of neighbour 17 of atom 1 + 1.0000000000000000 1.0000000000000000 -1.0000000000000000 + -2.9663166618997986E-004 0.0000000000000000 0.0000000000000000 + 0.0000000000000000 3.8237713166163131E-003 0.0000000000000000 + 0.0000000000000000 0.0000000000000000 -2.9663166618997986E-004 + 1 In the unit cell, what is the index of neighbour 18 of atom 1 + 1.0000000000000000 -1.0000000000000000 1.0000000000000000 + 3.8237713166163131E-003 0.0000000000000000 0.0000000000000000 + 0.0000000000000000 -2.9663166618997986E-004 0.0000000000000000 + 0.0000000000000000 0.0000000000000000 -2.9663166618997986E-004 + 1 In the unit cell, what is the index of neighbour 19 of atom 1 + 1.0000000000000000 -1.0000000000000000 -1.0000000000000000 + -2.9663166618997986E-004 0.0000000000000000 0.0000000000000000 + 0.0000000000000000 -2.9663166618997986E-004 0.0000000000000000 + 0.0000000000000000 0.0000000000000000 3.8237713166163131E-003 + 1 In the unit cell, what is the index of neighbour 20 of atom 1 + 0.0000000000000000 -2.0000000000000000 1.0000000000000000 + -9.4905718066452856E-005 -3.0927235457822169E-004 -9.6529816339358481E-005 + -3.0927235457822169E-004 5.8429860388881907E-004 3.0927235457822169E-004 + -9.6529816339358481E-005 3.0927235457822169E-004 -9.4905718066452856E-005 + 1 In the unit cell, what is the index of neighbour 21 of atom 1 + 0.0000000000000000 -1.0000000000000000 -1.0000000000000000 + -9.4905718066452856E-005 9.6529816339358481E-005 3.0927235457822169E-004 + 9.6529816339358481E-005 -9.4905718066452856E-005 3.0927235457822169E-004 + 3.0927235457822169E-004 3.0927235457822169E-004 5.8429860388881907E-004 + 1 In the unit cell, what is the index of neighbour 22 of atom 1 + 1.0000000000000000 1.0000000000000000 -2.0000000000000000 + -9.4905718066452856E-005 -3.0927235457822169E-004 9.6529816339358481E-005 + -3.0927235457822169E-004 5.8429860388881907E-004 -3.0927235457822169E-004 + 9.6529816339358481E-005 -3.0927235457822169E-004 -9.4905718066452856E-005 + 1 In the unit cell, what is the index of neighbour 23 of atom 1 + 1.0000000000000000 0.0000000000000000 1.0000000000000000 + 5.8429860388881907E-004 3.0927235457822169E-004 3.0927235457822169E-004 + 3.0927235457822169E-004 -9.4905718066452856E-005 9.6529816339358481E-005 + 3.0927235457822169E-004 9.6529816339358481E-005 -9.4905718066452856E-005 + 1 In the unit cell, what is the index of neighbour 24 of atom 1 + 0.0000000000000000 -1.0000000000000000 2.0000000000000000 + 5.8429860388881907E-004 -3.0927235457822169E-004 3.0927235457822169E-004 + -3.0927235457822169E-004 -9.4905718066452856E-005 -9.6529816339358481E-005 + 3.0927235457822169E-004 -9.6529816339358481E-005 -9.4905718066452856E-005 + 1 In the unit cell, what is the index of neighbour 25 of atom 1 + 1.0000000000000000 0.0000000000000000 -2.0000000000000000 + -9.4905718066452856E-005 -9.6529816339358481E-005 3.0927235457822169E-004 + -9.6529816339358481E-005 -9.4905718066452856E-005 -3.0927235457822169E-004 + 3.0927235457822169E-004 -3.0927235457822169E-004 5.8429860388881907E-004 + 1 In the unit cell, what is the index of neighbour 26 of atom 1 + 0.0000000000000000 1.0000000000000000 1.0000000000000000 + -9.4905718066452856E-005 9.6529816339358481E-005 3.0927235457822169E-004 + 9.6529816339358481E-005 -9.4905718066452856E-005 3.0927235457822169E-004 + 3.0927235457822169E-004 3.0927235457822169E-004 5.8429860388881907E-004 + 1 In the unit cell, what is the index of neighbour 27 of atom 1 + 0.0000000000000000 2.0000000000000000 -1.0000000000000000 + -9.4905718066452856E-005 -3.0927235457822169E-004 -9.6529816339358481E-005 + -3.0927235457822169E-004 5.8429860388881907E-004 3.0927235457822169E-004 + -9.6529816339358481E-005 3.0927235457822169E-004 -9.4905718066452856E-005 + 1 In the unit cell, what is the index of neighbour 28 of atom 1 + 1.0000000000000000 -2.0000000000000000 0.0000000000000000 + -9.4905718066452856E-005 -9.6529816339358481E-005 -3.0927235457822169E-004 + -9.6529816339358481E-005 -9.4905718066452856E-005 3.0927235457822169E-004 + -3.0927235457822169E-004 3.0927235457822169E-004 5.8429860388881907E-004 + 1 In the unit cell, what is the index of neighbour 29 of atom 1 + 1.0000000000000000 1.0000000000000000 0.0000000000000000 + -9.4905718066452856E-005 3.0927235457822169E-004 9.6529816339358481E-005 + 3.0927235457822169E-004 5.8429860388881907E-004 3.0927235457822169E-004 + 9.6529816339358481E-005 3.0927235457822169E-004 -9.4905718066452856E-005 + 1 In the unit cell, what is the index of neighbour 30 of atom 1 + 0.0000000000000000 1.0000000000000000 -2.0000000000000000 + 5.8429860388881907E-004 -3.0927235457822169E-004 3.0927235457822169E-004 + -3.0927235457822169E-004 -9.4905718066452856E-005 -9.6529816339358481E-005 + 3.0927235457822169E-004 -9.6529816339358481E-005 -9.4905718066452856E-005 + 1 In the unit cell, what is the index of neighbour 31 of atom 1 + 1.0000000000000000 -2.0000000000000000 1.0000000000000000 + 5.8429860388881907E-004 -3.0927235457822169E-004 -3.0927235457822169E-004 + -3.0927235457822169E-004 -9.4905718066452856E-005 9.6529816339358481E-005 + -3.0927235457822169E-004 9.6529816339358481E-005 -9.4905718066452856E-005 + 1 In the unit cell, what is the index of neighbour 32 of atom 1 + 2.0000000000000000 0.0000000000000000 -1.0000000000000000 + -9.4905718066452856E-005 3.0927235457822169E-004 -9.6529816339358481E-005 + 3.0927235457822169E-004 5.8429860388881907E-004 -3.0927235457822169E-004 + -9.6529816339358481E-005 -3.0927235457822169E-004 -9.4905718066452856E-005 + 1 In the unit cell, what is the index of neighbour 33 of atom 1 + 2.0000000000000000 -1.0000000000000000 -1.0000000000000000 + -9.4905718066452856E-005 9.6529816339358481E-005 -3.0927235457822169E-004 + 9.6529816339358481E-005 -9.4905718066452856E-005 -3.0927235457822169E-004 + -3.0927235457822169E-004 -3.0927235457822169E-004 5.8429860388881907E-004 + 1 In the unit cell, what is the index of neighbour 34 of atom 1 + -1.0000000000000000 0.0000000000000000 2.0000000000000000 + -9.4905718066452856E-005 -9.6529816339358481E-005 3.0927235457822169E-004 + -9.6529816339358481E-005 -9.4905718066452856E-005 -3.0927235457822169E-004 + 3.0927235457822169E-004 -3.0927235457822169E-004 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anharmonic_free_energy --temperature 14 --quantum -qg3ph 5 5 5 -qg4ph 5 5 5 -qgh 30 30 30 diff --git a/tests/anharmonic_free_energy/Neon_14K_quantum/infile.forceconstant b/tests/anharmonic_free_energy/Neon_14K_quantum/infile.forceconstant new file mode 100644 index 00000000..c2423f59 --- /dev/null +++ b/tests/anharmonic_free_energy/Neon_14K_quantum/infile.forceconstant @@ -0,0 +1,279 @@ + 1 How many atoms per unit cell + 6.331974629739952 Realspace cutoff (A) + 55 How many neighbours does atom 1 have + 1 In the unit cell, what is the index of neighbour 1 of atom 1 + 0.0000000000000000 0.0000000000000000 0.0000000000000000 + 0.12761135226416648 0.0000000000000000 0.0000000000000000 + 0.0000000000000000 0.12761135226416648 0.0000000000000000 + 0.0000000000000000 0.0000000000000000 0.12761135226416648 + 1 In the unit cell, what is the index of neighbour 2 of atom 1 + -1.0000000000000000 0.0000000000000000 1.0000000000000000 + 6.6794254861375017E-004 0.0000000000000000 0.0000000000000000 + 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a/tests/anharmonic_free_energy/Neon_14K_quantum/infile.ucposcar b/tests/anharmonic_free_energy/Neon_14K_quantum/infile.ucposcar new file mode 100644 index 00000000..a4c55880 --- /dev/null +++ b/tests/anharmonic_free_energy/Neon_14K_quantum/infile.ucposcar @@ -0,0 +1,9 @@ +POSCAR +4.4773821989528795 +0.500000000000 0.500000000000 0.000000000000 +0.000000000000 0.500000000000 0.500000000000 +0.500000000000 0.000000000000 0.500000000000 +Ne +1 +Direct +0.000000000000000 0.000000000000000 0.000000000000000 diff --git a/tests/anharmonic_free_energy/Silicon_1600K_classical/infile.forceconstant b/tests/anharmonic_free_energy/Silicon_1600K_classical/infile.forceconstant new file mode 100644 index 00000000..3480354c --- /dev/null +++ b/tests/anharmonic_free_energy/Silicon_1600K_classical/infile.forceconstant @@ -0,0 +1,175 @@ + 2 How many atoms per unit cell + 3.839589821895871 Realspace cutoff (A) + 17 How many neighbours does atom 1 have + 1 In the unit cell, what is the index of neighbour 1 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-0.10919224582373405 + 4.9423266512913018E-002 -4.9576827118800064E-002 0.10919224582373405 + 0.10919224582373405 -0.10919224582373405 0.24746210671238913 + 1 In the unit cell, what is the index of neighbour 8 of atom 1 + 0.0000000000000000 1.0000000000000000 0.0000000000000000 + 0.24746210671238913 0.10919224582373405 0.10919224582373405 + -0.10919224582373405 -4.9576827118800064E-002 -4.9423266512913018E-002 + -0.10919224582373405 -4.9423266512913018E-002 -4.9576827118800064E-002 + 1 In the unit cell, what is the index of neighbour 9 of atom 1 + 1.0000000000000000 -1.0000000000000000 0.0000000000000000 + -4.9576827118800064E-002 0.10919224582373405 4.9423266512913018E-002 + -0.10919224582373405 0.24746210671238913 0.10919224582373405 + 4.9423266512913018E-002 -0.10919224582373405 -4.9576827118800064E-002 + 1 In the unit cell, what is the index of neighbour 10 of atom 1 + 1.0000000000000000 0.0000000000000000 -1.0000000000000000 + 0.24746210671238913 -0.10919224582373405 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0.750000000000000 0.916666666666667 +0.916666666666667 0.916666666666667 0.750000000000000 diff --git a/tests/anharmonic_free_energy/Silicon_1600K_classical/infile.ucposcar b/tests/anharmonic_free_energy/Silicon_1600K_classical/infile.ucposcar new file mode 100644 index 00000000..3c904cb8 --- /dev/null +++ b/tests/anharmonic_free_energy/Silicon_1600K_classical/infile.ucposcar @@ -0,0 +1,11 @@ +Si Diamond +5.43 +0.500000000000 0.500000000000 0.000000000000 +0.000000000000 0.500000000000 0.500000000000 +0.500000000000 0.000000000000 0.500000000000 +Si +2 +direct coordinates +0.000000000000 0.000000000000 0.000000000000 +0.250000000000 0.250000000000 0.250000000000 + diff --git a/tests/anharmonic_free_energy/infile.forceconstant b/tests/anharmonic_free_energy/infile.forceconstant deleted file mode 120000 index 4b261f83..00000000 --- a/tests/anharmonic_free_energy/infile.forceconstant +++ /dev/null @@ -1 +0,0 @@ -../infiles/infile.forceconstant \ No newline at end of file diff --git a/tests/anharmonic_free_energy/infile.forceconstant_thirdorder b/tests/anharmonic_free_energy/infile.forceconstant_thirdorder deleted file mode 120000 index f544ade8..00000000 --- a/tests/anharmonic_free_energy/infile.forceconstant_thirdorder +++ /dev/null @@ -1 +0,0 @@ -../infiles/infile.forceconstant_thirdorder \ No newline at end of file diff --git a/tests/anharmonic_free_energy/infile.forces b/tests/anharmonic_free_energy/infile.forces deleted file mode 120000 index 347ec060..00000000 --- a/tests/anharmonic_free_energy/infile.forces +++ /dev/null @@ -1 +0,0 @@ -../infiles/infile.forces \ No newline at end of file diff --git a/tests/anharmonic_free_energy/infile.meta b/tests/anharmonic_free_energy/infile.meta deleted file mode 120000 index ef14956c..00000000 --- a/tests/anharmonic_free_energy/infile.meta +++ /dev/null @@ -1 +0,0 @@ -../infiles/infile.meta \ No newline at end of file diff --git a/tests/anharmonic_free_energy/infile.positions b/tests/anharmonic_free_energy/infile.positions deleted file mode 120000 index fcce51a5..00000000 --- a/tests/anharmonic_free_energy/infile.positions +++ /dev/null @@ -1 +0,0 @@ -../infiles/infile.positions \ No newline at end of file diff --git a/tests/anharmonic_free_energy/infile.ssposcar b/tests/anharmonic_free_energy/infile.ssposcar deleted file mode 120000 index 1cfa068d..00000000 --- a/tests/anharmonic_free_energy/infile.ssposcar +++ /dev/null @@ -1 +0,0 @@ -../infiles/infile.ssposcar \ No newline at end of file diff --git a/tests/anharmonic_free_energy/infile.stat b/tests/anharmonic_free_energy/infile.stat deleted file mode 120000 index 3e9aa633..00000000 --- a/tests/anharmonic_free_energy/infile.stat +++ /dev/null @@ -1 +0,0 @@ -../infiles/infile.stat \ No newline at end of file diff --git a/tests/anharmonic_free_energy/infile.ucposcar b/tests/anharmonic_free_energy/infile.ucposcar deleted file mode 120000 index b943f946..00000000 --- a/tests/anharmonic_free_energy/infile.ucposcar +++ /dev/null @@ -1 +0,0 @@ -../infiles/infile.ucposcar \ No newline at end of file diff --git a/tests/anharmonic_free_energy/reference/Argon_80K_classical_reference b/tests/anharmonic_free_energy/reference/Argon_80K_classical_reference new file mode 100644 index 00000000..9ed342af --- /dev/null +++ b/tests/anharmonic_free_energy/reference/Argon_80K_classical_reference @@ -0,0 +1,10 @@ +# Temperature: 0.800000000000E+02 + # Harmonic contribution + # Free energy [eV/at] Internal energy [eV/at] Entropy [kB] Heat capacity [kB] + -0.002161720125 0.020681592720 3.313571612390 3.000000000000 + # First Cumulant Contribution + # Free energy [eV/at] Internal energy [eV/at] Entropy [kB] Heat capacity [kB] + 0.000052542238 -0.000052542238 -0.015243188956 -0.015243188956 + # Second Cumulant Contribution + # Free energy [eV/at] Internal energy [eV/at] Entropy [kB] Heat capacity [kB] + -0.000757328812 0.000757328812 0.219710973722 0.219710973722 diff --git a/tests/anharmonic_free_energy/reference/Neon_14K_quantum_reference b/tests/anharmonic_free_energy/reference/Neon_14K_quantum_reference new file mode 100644 index 00000000..7b44cffe --- /dev/null +++ b/tests/anharmonic_free_energy/reference/Neon_14K_quantum_reference @@ -0,0 +1,10 @@ +# Temperature: 0.140000000000E+02 + # Harmonic contribution + # Free energy [eV/at] Internal energy [eV/at] Entropy [kB] Heat capacity [kB] + 0.007257533994 0.007761992603 0.418142934371 0.987045346630 + # First Cumulant Contribution + # Free energy [eV/at] Internal energy [eV/at] Entropy [kB] Heat capacity [kB] + 0.000070677388 0.000063045856 -0.006325734499 -0.023459532844 + # Second Cumulant Contribution + # Free energy [eV/at] Internal energy [eV/at] Entropy [kB] Heat capacity [kB] + -0.000195310263 -0.000040784905 0.128085209130 0.242479458040 diff --git a/tests/anharmonic_free_energy/reference/Silicon_1600K_classical_reference b/tests/anharmonic_free_energy/reference/Silicon_1600K_classical_reference new file mode 100644 index 00000000..b87c6fc2 --- /dev/null +++ b/tests/anharmonic_free_energy/reference/Silicon_1600K_classical_reference @@ -0,0 +1,10 @@ +# Temperature: 0.160000000000E+04 + # Harmonic contribution + # Free energy [eV/at] Internal energy [eV/at] Entropy [kB] Heat capacity [kB] + -0.515229485446 0.413631854400 6.736869972408 3.000000000000 + # First Cumulant Contribution + # Free energy [eV/at] Internal energy [eV/at] Entropy [kB] Heat capacity [kB] + -0.000543896863 0.000543896863 0.007889578969 0.007889578969 + # Second Cumulant Contribution + # Free energy [eV/at] Internal energy [eV/at] Entropy [kB] Heat capacity [kB] + -0.002515013780 0.002515013780 0.036481916272 0.036481916272 diff --git a/tests/anharmonic_free_energy/reference/outfile.anharmonic_free_energy b/tests/anharmonic_free_energy/reference/outfile.anharmonic_free_energy deleted file mode 100644 index df17a2d4..00000000 --- a/tests/anharmonic_free_energy/reference/outfile.anharmonic_free_energy +++ /dev/null @@ -1,5 +0,0 @@ - # Free energy at -314.16 K, unit : eV/atom - # Lowest order (1st order cumulant, 2nd order cumulant) - -3744.84683 -3744.84683 - # Third order anharmonic corrections (1st order cumulant, 2nd order cumulant) - -3744.84770 -3744.84770 diff --git a/tests/anharmonic_free_energy/test_anharmonic_free_energy.py b/tests/anharmonic_free_energy/test_anharmonic_free_energy.py index a749cb70..94479b83 100644 --- a/tests/anharmonic_free_energy/test_anharmonic_free_energy.py +++ b/tests/anharmonic_free_energy/test_anharmonic_free_energy.py @@ -1,21 +1,49 @@ import numpy as np +import pytest from pathlib import Path parent = Path(__file__).parent folder = parent / "reference" +cases = [ + "Silicon_1600K_classical", + "Neon_14K_quantum", +] +output_file = "outfile.anharmonic_thermodynamics" +# Seems to be some noise due to ordering of sums. +rtol = 1e-6 +atol = 1e-8 def _read_file(file): - data = np.loadtxt(file) - return data - - -def test_output(file="outfile.anharmonic_free_energy"): - data_ref = _read_file(folder / file) - data_new = _read_file(parent / file) - - np.testing.assert_allclose(data_ref, data_new, err_msg=(parent / file).absolute()) + values = [] + with open(file, encoding="utf-8") as f: + for line in f: + stripped = line.strip() + if not stripped or stripped.startswith("#"): + continue + row = np.fromstring(stripped, sep=" ") + if row.size: + values.extend(row.tolist()) + return np.asarray(values, dtype=float) + + +@pytest.mark.parametrize("case", cases) +def test_output(case): + file_ref = folder / f"{case}_reference" + file_new = parent / case / output_file + data_ref = _read_file(file_ref) + data_new = _read_file(file_new) + + assert data_ref.shape == data_new.shape, file_new.absolute() + np.testing.assert_allclose( + data_ref, + data_new, + rtol=rtol, + atol=atol, + err_msg=str(file_new.absolute()), + ) if __name__ == "__main__": - test_output() + for case in cases: + test_output(case)