diff --git a/README.md b/README.md index 9ee3d3f39..a4bb10952 100644 --- a/README.md +++ b/README.md @@ -166,6 +166,7 @@ features reality: - P. Pracht ([@pprcht](https://github.com/pprcht)) - F. Pultar ([@pultar](https://github.com/pultar)) - J. Seibert ([@liljay42](https://github.com/liljay42)) +- L. M. Seidler ([@lmseidler](https://github.com/lmseidler)) - P. Shushkov - S. Spicher ([@sespic](https://github.com/sespic)) - M. Stahn ([@MtoLStoN](https://github.com/mtolston)) @@ -245,6 +246,10 @@ for ONIOM refer to: - C. Plett, A. Katbashev, S. Ehlert, S. Grimme, M. Bursch, *Phys. Chem. Chem. Phys.*, **2023**, 25, 17860-17868. DOI: [10.1039/D3CP02178E](https://doi.org/10.1039/D3CP02178E) +for O1NumHess refer to: +- B. Wang, S. Luo, Z. Wang, W. Liu, *J. Chem. Theory Comput.* **2025**, 21, 10893-10909. + DOI: 10.1021/acs.jctc.5c01354 + All references are available in [bibtex format](./assets/references.bib). diff --git a/assets/references.bib b/assets/references.bib index 2a6a3e418..182905844 100644 --- a/assets/references.bib +++ b/assets/references.bib @@ -203,3 +203,14 @@ @article{grimme_non-self-consistent_2023 pages = {124111}, file = {Full Text PDF:/Users/marcelmueller/Zotero/storage/LRJJ6T9I/Grimme et al. - 2023 - A non-self-consistent tight-binding electronic str.pdf:application/pdf;Snapshot:/Users/marcelmueller/Zotero/storage/FAT76IUH/A-non-self-consistent-tight-binding-electronic.html:text/html}, } + +@article{wang2025o1numhess, + title={O1NumHess: a fast and accurate seminumerical Hessian algorithm using only O (1) gradients}, + author={Wang, Bo and Luo, Shaohang and Wang, Zikuan and Liu, Wenjian}, + journal={J{.} Chem{.} Theory Comput{.}}, + volume={21}, + number={21}, + pages={10893--10909}, + year={2025}, + publisher={ACS Publications} +} diff --git a/man/xtb.1.adoc b/man/xtb.1.adoc index e1d208679..96456af28 100644 --- a/man/xtb.1.adoc +++ b/man/xtb.1.adoc @@ -234,6 +234,9 @@ NOTE: You can only select *one* runtyp, only the first runtyp will be used perform a biased numerical hessian calculation on an `ancopt(3)` optimized geometry +*--o1nh*:: + perform the numerical hessian calculation using the ODLR approximation (O1NumHess) + *--md*:: molecular dynamics simulation on start geometry diff --git a/src/CMakeLists.txt b/src/CMakeLists.txt index 47138c71a..ec9203bdd 100644 --- a/src/CMakeLists.txt +++ b/src/CMakeLists.txt @@ -110,6 +110,7 @@ list(APPEND srcs "${dir}/modef.f90" "${dir}/model_hessian.f90" "${dir}/neighbor.f90" + "${dir}/o1numhess.f90" "${dir}/onetri.f90" "${dir}/oniom.f90" "${dir}/optimizer.f90" diff --git a/src/hessian.F90 b/src/hessian.F90 index 331a800ae..ae4ad9618 100644 --- a/src/hessian.F90 +++ b/src/hessian.F90 @@ -113,6 +113,9 @@ subroutine numhess( & real(wp),allocatable :: amass_au(:), amass_amu(:) real(wp) :: asq, gamsq + ! final residual error in approximating gradients using odlr hessian + real(wp) :: final_err + type(TMolecule) :: tmol logical :: ex,rd @@ -139,6 +142,7 @@ subroutine numhess( & rd=.false. xyzsave = mol%xyz + ! TODO: need to figure out why this is done step=0.0001_wp call rotmol(mol%n,mol%xyz,step,2.*step,3.*step) @@ -185,7 +189,13 @@ subroutine numhess( & !! ======================================================================== ! Hessian part ----------------------------------------------------------- - if(freezeset%n.gt.0) then + if (set%o1numhess) then + h = 0.0_wp + call calc%odlrhessian(env, mol, chk0, step, h, final_err) + call env%check(exitRun) + if (exitRun) return + write(env%unit, '(A,1X,ES12.4)') "Error norm for predicted gradient (ODLR Hessian):", final_err + else if(freezeset%n.gt.0) then ! for frozfc of about 10 the frozen modes ! approach 5000 cm-1, i.e., come too close to ! the real ones @@ -212,7 +222,6 @@ subroutine numhess( & dipd = 0.0_wp pold = 0.0_wp call calc%hessian(env, mol, chk0, indx(:nonfrozh), step, h, dipd) - else !! ------------------------------------------------------------------------ ! normal case @@ -461,7 +470,8 @@ subroutine numhess( & ! for non-linear systems unless one fixes three atoms defines plane, 1 degree of freedom will exist, otherwise there should be 0 degrees of freedom ! anyway, the check here will become more complex and therefore it is not impemented ! NOTE: it is not necessary lowest N frequencies - error stop "not implemented" + call env%error("check for <=2 frozen atoms not implemented", source) + return ! for three atom systems we assume that the plane was constructed (or linear system is used) endif j=kend @@ -498,57 +508,60 @@ subroutine numhess( & res%rmass(i)= 1.0_wp / xsum enddo - !--- IR intensity ---! (holds in a similar fashion also for Raman) - ! 1. res%hess corresponds to the orthonormal eigenvectors of the mass-weighted Hessian - ! matrix (-> normal modes of vibration). By mass-weighting the Hessian matrix, - ! the normal modes are transformed into the mass-weighted space ("Q basis"), and - ! have the units [sqrt(mass) * length] - ! To obtain purely cartesian coordinates (-> transforming back into the Cartesian space), - ! the mass-weighted normal modes have to be divided by the square root of the mass of the respective atom. - ! - ! 2. res%hess(j,i) is the matrix which transforms a derivative with - ! respect to the j-th cartesian coordinate ("dipd") into a derivative with - ! respect to the i-th normal coordinate. - ! - ! 3. amass_au(j) = 1/sqrt(m(j)); m(j) is given in atomic units (a.u.). - ! - ! 4. matmul(D x H) = U - ! - ! 5. D = dipd(3,n3); H = res%hess(n3:n3); U = Matrix with dipol derivatives - ! in x, y and z direction per mode - ! - ! Generally nice reads for understanding the necessity of mass-weighting: - ! 1) https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Maps/ - ! Advanced_Theoretical_Chemistry_(Simons)/ - ! 03%3A_Characteristics_of_Energy_Surfaces/3.02%3A_Normal_Modes_of_Vibration - ! 2) https://www.cup.uni-muenchen.de/ch/compchem/G98vib.pdf - - do i = 1, n3 - do k = 1, 3 - sum2 = 0.0_wp - do j = 1, n3 - sum2 = sum2 + dipd(k,j)*(res%hess(j,i)*amass_au(j)) - end do - trdip(k) = sum2 - end do - res%dipt(i) = autokmmol*(trdip(1)**2+trdip(2)**2+trdip(3)**2) - end do - ! Raman activities (for intensities, see "write_tm_vibspectrum") - if (set%elprop == p_elprop_alpha) then + ! odlr hessian check, cannot calculate IR intensities + if (.not. set%o1numhess) then + !--- IR intensity ---! (holds in a similar fashion also for Raman) + ! 1. res%hess corresponds to the orthonormal eigenvectors of the mass-weighted Hessian + ! matrix (-> normal modes of vibration). By mass-weighting the Hessian matrix, + ! the normal modes are transformed into the mass-weighted space ("Q basis"), and + ! have the units [sqrt(mass) * length] + ! To obtain purely cartesian coordinates (-> transforming back into the Cartesian space), + ! the mass-weighted normal modes have to be divided by the square root of the mass of the respective atom. + ! + ! 2. res%hess(j,i) is the matrix which transforms a derivative with + ! respect to the j-th cartesian coordinate ("dipd") into a derivative with + ! respect to the i-th normal coordinate. + ! + ! 3. amass_au(j) = 1/sqrt(m(j)); m(j) is given in atomic units (a.u.). + ! + ! 4. matmul(D x H) = U + ! + ! 5. D = dipd(3,n3); H = res%hess(n3:n3); U = Matrix with dipol derivatives + ! in x, y and z direction per mode + ! + ! Generally nice reads for understanding the necessity of mass-weighting: + ! 1) https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Maps/ + ! Advanced_Theoretical_Chemistry_(Simons)/ + ! 03%3A_Characteristics_of_Energy_Surfaces/3.02%3A_Normal_Modes_of_Vibration + ! 2) https://www.cup.uni-muenchen.de/ch/compchem/G98vib.pdf + do i = 1, n3 - do k = 1,6 + do k = 1, 3 sum2 = 0.0_wp do j = 1, n3 - sum2 = sum2 + (res%hess(j,i)*amass_au(j))*dalphadr(k,j) + sum2 = sum2 + dipd(k,j)*(res%hess(j,i)*amass_au(j)) + end do + trdip(k) = sum2 + end do + res%dipt(i) = autokmmol*(trdip(1)**2+trdip(2)**2+trdip(3)**2) + end do + ! Raman activities (for intensities, see "write_tm_vibspectrum") + if (set%elprop == p_elprop_alpha) then + do i = 1, n3 + do k = 1,6 + sum2 = 0.0_wp + do j = 1, n3 + sum2 = sum2 + (res%hess(j,i)*amass_au(j))*dalphadr(k,j) + enddo + dalphadq(k,i) = sum2 enddo - dalphadq(k,i) = sum2 + asq = (dalphadq(1,i)+dalphadq(3,i)+dalphadq(6,i))**2 / 9.0_wp + gamsq = ( (dalphadq(1,i)-dalphadq(3,i))**2 + (dalphadq(3,i)-dalphadq(6,i))**2 + (dalphadq(6,i)-dalphadq(1,i))**2 & + & + 6.0_wp*(dalphadq(2,i)**2 + dalphadq(5,i)**2 + dalphadq(4,i)**2) )*0.5_wp + res%polt(i) = (45.0_wp*asq + 7.0_wp*gamsq) + res%polt(i) = res%polt(i) * autoaa4byamu() enddo - asq = (dalphadq(1,i)+dalphadq(3,i)+dalphadq(6,i))**2 / 9.0_wp - gamsq = ( (dalphadq(1,i)-dalphadq(3,i))**2 + (dalphadq(3,i)-dalphadq(6,i))**2 + (dalphadq(6,i)-dalphadq(1,i))**2 & - & + 6.0_wp*(dalphadq(2,i)**2 + dalphadq(5,i)**2 + dalphadq(4,i)**2) )*0.5_wp - res%polt(i) = (45.0_wp*asq + 7.0_wp*gamsq) - res%polt(i) = res%polt(i) * autoaa4byamu() - enddo + end if end if end subroutine numhess diff --git a/src/main/property.F90 b/src/main/property.F90 index 637cfaa19..a8c7cd1c4 100644 --- a/src/main/property.F90 +++ b/src/main/property.F90 @@ -652,25 +652,26 @@ subroutine main_freq & write (iunit, '(1x,a)') 'reduced masses (amu)' write (iunit, '(6(i5,'':'',f10.2))') (i, res%rmass(i), i=1, res%n3) - write (iunit, '(1x,a)') 'IR intensities (km·mol⁻¹)' - write (iunit, '(6(i5,'':'',f10.2))') (i, res%dipt(i), i=1, res%n3) - write (iunit, '(1x,a)') 'Raman intensities (Ä⁴*amu⁻¹)' - write (iunit, '(6(i5,'':'',f10.2))') (i, res%polt(i), i=1, res%n3) - - call open_file(ifile, 'vibspectrum', 'w') - if (set%elprop == p_elprop_alpha) then - call write_tm_vibspectrum(ifile, res%n3, res%freq, res%dipt, res%polt,& - set%ptbsetup%raman_temp, set%ptbsetup%raman_lambda) - else - call write_tm_vibspectrum(ifile, res%n3, res%freq, res%dipt, res%polt) + if (.not. set%o1numhess) then + write (iunit, '(1x,a)') 'IR intensities (km·mol⁻¹)' + write (iunit, '(6(i5,'':'',f10.2))') (i, res%dipt(i), i=1, res%n3) + write (iunit, '(1x,a)') 'Raman intensities (Ä⁴*amu⁻¹)' + write (iunit, '(6(i5,'':'',f10.2))') (i, res%polt(i), i=1, res%n3) + call open_file(ifile, 'vibspectrum', 'w') + if (set%elprop == p_elprop_alpha) then + call write_tm_vibspectrum(ifile, res%n3, res%freq, res%dipt, res%polt,& + set%ptbsetup%raman_temp, set%ptbsetup%raman_lambda) + else + call write_tm_vibspectrum(ifile, res%n3, res%freq, res%dipt, res%polt) + end if + call close_file(ifile) + write (iunit, '(1x,a)') 'output can be read by thermo (or use thermo option).' + write (iunit, '(1x,a)') 'writing molden fake output.' + write (iunit, '(1x,a)') & + & 'recommended (thermochemical) frequency scaling factor: 1.0' + call g98fake2('g98.out', mol%n, mol%at, mol%xyz, res%freq, res%rmass, res%dipt, res%hess) end if - call close_file(ifile) - write (iunit, '(1x,a)') 'output can be read by thermo (or use thermo option).' - write (iunit, '(1x,a)') 'writing molden fake output.' - write (iunit, '(1x,a)') & - & 'recommended (thermochemical) frequency scaling factor: 1.0' - call g98fake2('g98.out', mol%n, mol%at, mol%xyz, res%freq, res%rmass, res%dipt, res%hess) if (set%pr_nmtm) then call open_file(ifile, "vib_normal_modes", 'w') diff --git a/src/meson.build b/src/meson.build index 30e5e274a..65937cd8a 100644 --- a/src/meson.build +++ b/src/meson.build @@ -108,6 +108,7 @@ srcs += files( 'modef.f90', 'model_hessian.f90', 'neighbor.f90', + 'o1numhess.f90', 'onetri.f90', 'oniom.f90', 'optimizer.f90', diff --git a/src/o1numhess.f90 b/src/o1numhess.f90 new file mode 100644 index 000000000..c8b603de5 --- /dev/null +++ b/src/o1numhess.f90 @@ -0,0 +1,981 @@ +! This file is part of xtb. +! +! Copyright (C) 2026 Leopold M. Seidler +! +! xtb is free software: you can redistribute it and/or modify it under +! the terms of the GNU Lesser General Public License as published by +! the Free Software Foundation, either version 3 of the License, or +! (at your option) any later version. +! +! xtb is distributed in the hope that it will be useful, +! but WITHOUT ANY WARRANTY; without even the implied warranty of +! MERCHANTABILITY or FITNESS FOR A PARTICULAR PURPOSE. See the +! GNU Lesser General Public License for more details. +! +! You should have received a copy of the GNU Lesser General Public License +! along with xtb. If not, see . + +!> O1 numerical Hessian utilities +!> Ref: https://doi.org/10.1021/acs.jctc.5c01354 +module xtb_o1numhess + use xtb_mctc_accuracy, only : wp + use xtb_mctc_convert, only : autoaa + use xtb_mctc_blas, only : mctc_gemm, mctc_nrm2, mctc_dot + use xtb_type_environment, only : TEnvironment + use xtb_param_covalentrad, only : get_cov_rad + implicit none + private + + public :: adj_list + public :: gen_local_hessian, lr_loop, get_neighbor_list, gen_displdir, swart + + type :: adj_list + integer, allocatable :: neighbors(:) + end type adj_list + + abstract interface + subroutine matvec_operator(x, y, env, ctx) + import :: wp, TEnvironment + real(wp), intent(in) :: x(:) + real(wp), intent(inout) :: y(:) + type(TEnvironment), intent(inout) :: env + class(*), optional, target, intent(inout) :: ctx + end subroutine matvec_operator + end interface + + type :: odlr_operator_data + integer :: N, ndispl_final, info + logical, allocatable :: mask(:, :) + real(wp), pointer :: displdir(:, :) => null() + real(wp), allocatable :: W2(:, :) + + real(wp), allocatable :: tmp(:, :) + real(wp), allocatable :: tmp2(:, :) + real(wp), allocatable :: f1(:, :) + real(wp), allocatable :: f2(:, :) + end type odlr_operator_data + + character(len=*), parameter :: source = 'xtb_o1numhess' + +contains + +!> Main routine to recover local Hessian +subroutine gen_local_hessian(env, ndispl_final, distmat, displdir, g, dmax, hess_out) + !> Calculation environment + type(TEnvironment), intent(inout) :: env + !> Number of displacements + integer, intent(in) :: ndispl_final + !> Distance matrix between atoms + real(wp), intent(in) :: distmat(:, :) + !> Displacement directions + real(wp), intent(in), target :: displdir(:, :) + !> Gradient derivatives + real(wp), intent(in) :: g(:, :) + !> Maximum distance threshold + real(wp), intent(in) :: dmax + !> Output Hessian matrix + real(wp), intent(out) :: hess_out(:, :) + + real(wp), parameter :: lam = 1.0e-2_wp, bet = 1.5_wp, ddmax = 5.0_wp + + ! Local work arrays + type(odlr_operator_data) :: ctx + real(wp), allocatable :: rhs(:, :), rhsv(:), sol(:) + integer :: i, ndim, N, info + logical :: terminate_run + + N = size(distmat, 1) + + ! Prepare cache + ctx%N = N + ctx%ndispl_final = ndispl_final + allocate(ctx%f1(N, N), ctx%f2(N, N), ctx%tmp(N, N), ctx%tmp2(N, ndispl_final)) + ctx%displdir => displdir + + ! Calculate Regularization Term W2 + ctx%W2 = lam * max(0.0_wp, distmat(:, :) - dmax)**(2.0_wp * bet) + + ! Calculate rhs + allocate(rhs(N, N)) + rhs = 0.0_wp + call mctc_gemm(g(:, :ndispl_final), displdir(:, :ndispl_final), rhs, transb="t") + + ! Masks and Packing + allocate(ctx%mask(N, N)) + ctx%mask = (distmat < (dmax + ddmax)) + do i = 2, N + ctx%mask(i, 1:i-1) = .false. + end do + + ! RHS Vector (b in Ax=b) + rhsv = pack_sym(rhs, ctx%mask) + ndim = size(rhsv) + + ! Solve + allocate(sol(ndim)) + sol = 0.0_wp + info = 0 + call cg(env, odlr_operator, ndim, rhsv, sol, info, ctx=ctx) + call env%check(terminate_run) + if (info == 1) then + call env%warning("local hessian: CG failed to converge", source) + else if (terminate_run) then + return + end if + + ! Recover Hessian from solution + hess_out = unpack_sym(sol, ctx%mask, N) +end subroutine gen_local_hessian + +!> Defines the linear operator for defining the optimizational +!> problem in local Hessian calculation +subroutine odlr_operator(x, y, env, ctx) + real(wp), intent(in) :: x(:) + real(wp), intent(inout) :: y(:) + type(TEnvironment), intent(inout) :: env + class(*), optional, target, intent(inout) :: ctx + + type(odlr_operator_data), pointer :: op_data + + if (present(ctx)) then + select type(ctx) + type is (odlr_operator_data) + op_data => ctx + class default + call env%error("odlr_operator: invalid context", source) + return + end select + else + call env%error("odlr_operator: missing context", source) + return + end if + + op_data%tmp = unpack_sym(x, op_data%mask, op_data%N) + + call mctc_gemm(op_data%tmp, op_data%displdir(:, :op_data%ndispl_final), op_data%tmp2) + call mctc_gemm(op_data%tmp2, op_data%displdir(:, :op_data%ndispl_final), op_data%f1, transb="t") + + op_data%f1 = (op_data%f1 + transpose(op_data%f1)) / 2.0_wp + op_data%f2 = op_data%W2 * op_data%tmp + + y = pack_sym(op_data%f1 + op_data%f2, op_data%mask) +end subroutine odlr_operator + +!> Generic Conjugate Gradient Solver +subroutine cg(env, operator, ndim, rhs, x, info, x0, ctx) + type(TEnvironment), intent(inout) :: env + procedure(matvec_operator) :: operator + integer, intent(in) :: ndim + real(wp), intent(in) :: rhs(:) + real(wp), intent(inout) :: x(:) + integer, intent(out) :: info + real(wp), intent(in), optional :: x0(:) + class(*), optional, target, intent(inout) :: ctx + + integer, parameter :: max_iter = 1000 + real(wp), parameter :: tol = 1.0e-14_wp + real(wp), allocatable :: r(:), p(:), Ap(:) + real(wp) :: alpha, beta, rs_old, rs_new + integer :: k + logical :: terminate_run + + allocate(r(ndim), p(ndim), Ap(ndim)) + + if (present(x0)) then + call operator(x, Ap, env, ctx) + r = rhs - Ap + else + r = rhs + end if + p = r + rs_old = mctc_dot(r, r) + + do k = 1, max_iter + call operator(p, Ap, env, ctx) + call env%check(terminate_run) + if (terminate_run) return + + alpha = rs_old / mctc_dot(p, Ap) + x = x + alpha * p + r = r - alpha * Ap + rs_new = mctc_dot(r, r) + + if (rs_new < tol) exit + + beta = rs_new / rs_old + p = r + beta * p + rs_old = rs_new + end do + + if (k == max_iter) then + info = 1 + else + info = 0 + end if +end subroutine cg + +!> Corrects Hessian hnum using a symmetric, low-rank update +!> so that g approx hnum * displdir +subroutine lr_loop(env, ndispl, g, hess_out, displdir, final_err) + type(TEnvironment), intent(inout) :: env + integer, intent(in) :: ndispl + real(wp), intent(in) :: g(:, :) ! Input Gradients + real(wp), intent(inout) :: hess_out(:, :) ! Hessian to correct + real(wp), intent(in) :: displdir(:, :) ! Displacement directions + real(wp), intent(out) :: final_err ! Final residual error + + real(wp), parameter :: mingrad_LR = 1.0e-3_wp + real(wp), parameter :: thresh_LR = 1.0e-8_wp + integer, parameter :: maxiter_LR = 100 + + ! Local variables + real(wp), allocatable :: resid(:, :), hcorr(:, :), tmp(:, :) + real(wp) :: dampfac, err0, err, norm_g + integer :: it, N + + N = size(g, 1) + + dampfac = 1.0_wp + err0 = huge(1.0_wp) + + norm_g = mctc_nrm2(g(:, :ndispl)) + + allocate(hcorr(N, N), tmp(N, N)) + ! 2. Iterative Correction Loop + loop_lr: do it = 1, maxiter_LR + + call mctc_gemm(hess_out, displdir(:, :ndispl), tmp) + resid = g(:, :ndispl) - tmp + + err = mctc_nrm2(resid) + + if (err < thresh_LR) then + ! Converged successfully + exit loop_lr + + else if (abs(err - err0) < thresh_LR * err0) then + ! print *, 'Warning: Gradients cannot be reproduced by symmetric Hessian (Stagnation).' + exit loop_lr + + else if (err > err0 .and. err > norm_g) then + ! Divergence detected + dampfac = dampfac * 0.5_wp + end if + + ! hcorr = matmul(resid, transpose(displdir(:, :ndispl))) + call mctc_gemm(resid, displdir(:, :ndispl), hcorr, transb="t") + hcorr = 0.5_wp * (hcorr + transpose(hcorr)) + hess_out = hess_out + dampfac * hcorr + + err0 = err + + end do loop_lr + + if (it == maxiter_LR) then + call env%warning("LR loop failed to converge", source) + end if + + final_err = err + +end subroutine lr_loop + +!> Helper to unpack vector to Symmetric Matrix +function unpack_sym(v, mask, n) result(H) + real(wp), intent(in) :: v(:) + logical, intent(in) :: mask(n, n) + integer, intent(in) :: n + real(wp) :: H(n, n) + integer :: i + + H = 0.0_wp + H = unpack(v, mask, field=0.0_wp) + + ! Symmetrize + do i = 2, n + H(i, 1:i-1) = H(1:i-1, i) + end do +end function unpack_sym + +!> Helper to pack symmetric matrix +function pack_sym(m, mask) result(v) + real(wp), intent(in) :: m(:, :) + logical, intent(in) :: mask(:, :) + real(wp), allocatable :: v(:) + + ! symmetrize, then pack + v = pack((m + transpose(m)) * 0.5_wp, mask) +end function pack_sym + +!> Setup a neighbor list based on a given distante matrix +subroutine get_neighbor_list(distmat, dmax, nblist) + real(wp), intent(in) :: distmat(:, :) + real(wp), intent(in) :: dmax + type(adj_list), allocatable, intent(out) :: nblist(:) + + integer, allocatable :: labels(:) + real(wp), allocatable :: comp_dist(:, :) + integer, allocatable :: mst_matrix(:, :) + real(wp) :: d, min_d + real(wp), parameter :: eps = 1.0e-8_wp + integer :: i, j, ncomp, N, li, lj + + N = size(distmat, 1) + allocate(nblist(N)) + + ! 1. Calculate Initial Neighbors + do i = 1, N + do j = 1, N + d = distmat(i, j) + if (d < dmax) then + call add_neighbor(nblist(i), j) + end if + end do + end do + + ! 2. Identify Connected Components (DFS) + allocate(labels(N)) + labels = 0 + ncomp = 0 + + do i = 1, N + if (labels(i) == 0) then + ncomp = ncomp + 1 + call dfs_label(i, N, nblist, labels, ncomp) + end if + end do + + if (ncomp == 1) return ! Graph is already connected + + ! 3. Distance between components + ! For every pair of components, find the minimum distance + allocate(comp_dist(ncomp, ncomp)) + comp_dist = huge(1.0_wp) + + !$omp parallel do default(none) schedule(runtime) & + !$omp shared(N, distmat, labels, comp_dist) & + !$omp private(i, j, d, li, lj) + do i = 1, N - 1 + li = labels(i) + do j = i + 1, N + lj = labels(j) + if (li /= lj) then + d = distmat(i, j) + !$omp atomic update + comp_dist(li, lj) = min(comp_dist(li, lj), d) + !$omp atomic update + comp_dist(lj, li) = min(comp_dist(lj, li), d) + end if + end do + end do + + ! 4. Minimum Spanning Tree (Prim's Algorithm) on Components + ! Returns symmetric matrix: 1 if connected in MST, 0 otherwise + call prim_mst(ncomp, comp_dist, mst_matrix) + + ! 5. Stitching: Add necessary links closer than MST distance + eps + do i = 1, N - 1 + do j = i + 1, N + if (labels(i) /= labels(j)) then + ! If these components are connected in the MST + if (mst_matrix(labels(i), labels(j)) == 1) then + ! Get the min distance required to bridge them + min_d = comp_dist(labels(i), labels(j)) + + ! If this pair provides that bridge (handling degeneracy) + if (distmat(i, j) <= min_d + eps) then + call add_neighbor_unique(nblist(i), j) + call add_neighbor_unique(nblist(j), i) + end if + end if + end if + end do + end do +end subroutine get_neighbor_list + +!> Helper to add neighbors to dynamic array +subroutine add_neighbor(list, val) + type(adj_list), intent(inout) :: list + integer, intent(in) :: val + integer, allocatable :: tmp(:) + integer :: sz + + if (.not. allocated(list%neighbors)) then + allocate(list%neighbors(1)) + list%neighbors(1) = val + else + sz = size(list%neighbors) + allocate(tmp(sz + 1)) + tmp(1:sz) = list%neighbors + tmp(sz + 1) = val + call move_alloc(tmp, list%neighbors) + end if +end subroutine add_neighbor + +!> Helper to add neighbors to dynamic array if not present +subroutine add_neighbor_unique(list, val) + type(adj_list), intent(inout) :: list + integer, intent(in) :: val + integer :: k + + if (allocated(list%neighbors)) then + do k = 1, size(list%neighbors) + if (list%neighbors(k) == val) return + end do + end if + call add_neighbor(list, val) +end subroutine add_neighbor_unique + +!> Helper to recursive DFS for labeling +recursive subroutine dfs_label(u, n, nblist, labels, comp_id) + integer, intent(in) :: u, n, comp_id + type(adj_list), intent(in) :: nblist(:) + integer, intent(inout) :: labels(:) + integer :: k, v + + labels(u) = comp_id + if (.not. allocated(nblist(u)%neighbors)) return + + do k = 1, size(nblist(u)%neighbors) + v = nblist(u)%neighbors(k) + if (labels(v) == 0) then + call dfs_label(v, n, nblist, labels, comp_id) + end if + end do +end subroutine dfs_label + +!> Setup an adjacency matrix based on a given distance matrix +!> using Prim's algorithm for a minimum spanning tree +subroutine prim_mst(nc, dists, adj_mst) + integer, intent(in) :: nc + real(wp), intent(in) :: dists(nc, nc) + integer, allocatable, intent(out) :: adj_mst(:, :) + + real(wp) :: min_val, key(nc) + integer :: parent(nc) + logical :: mst_set(nc) + integer :: i, count, u, v + + allocate(adj_mst(nc, nc)) + adj_mst = 0 + + key = huge(1.0_wp) + parent = 0 + mst_set = .false. + + key(1) = 0.0_wp + parent(1) = -1 + + do count = 1, nc - 1 + ! Pick minimum key vertex not yet including in MST + min_val = huge(1.0_wp) + u = -1 + do i = 1, nc + if (.not. mst_set(i) .and. key(i) < min_val) then + min_val = key(i) + u = i + end if + end do + + if (u == -1) exit + mst_set(u) = .true. + + ! Update adjacent vertices + do v = 1, nc + if (dists(u, v) > 0.0_wp .and. .not. mst_set(v) .and. dists(u, v) < key(v)) then + parent(v) = u + key(v) = dists(u, v) + end if + end do + end do + + ! Convert parent array to adjacency matrix + do i = 2, nc + if (parent(i) /= -1) then + adj_mst(i, parent(i)) = 1 + adj_mst(parent(i), i) = 1 + end if + end do +end subroutine prim_mst + +!> Calculate displacement vectors for the gradient derivatives +subroutine gen_displdir(n, ndispl0, h0, max_nb, nblist, nbcounts, & + eps, eps2, displdir, ndispl_final) + integer, intent(in) :: n, ndispl0, max_nb + !> Initial guess Hessian + real(wp), intent(in) :: h0(n,n) + !> Neighbor list + type(adj_list), intent(in) :: nblist(:) + !> Number of neighbors per atom + integer, intent(in) :: nbcounts(n) + !> Thresholds for sign determination and convergence + real(wp), intent(in) :: eps, eps2 + !> Displacement directions + real(wp), intent(inout) :: displdir(n, n) + !> Final number of displacements + integer, intent(out) :: ndispl_final + + ! Local variables + integer :: i, j, k, p, q, nnb, info, n_curr, idx, locind + integer :: nb_idx(max_nb) + real(wp) :: ev(n), coverage(n), locev(max_nb) + real(wp), allocatable :: eye(:, :) + real(wp) :: loceigs(max_nb) + real(wp) :: norm_ev1, norm_ev2, v_norm, d_dot + real(wp), allocatable :: locev_store(:, :) + logical :: done + ! Thread-private work arrays for parallel region + real(wp), allocatable :: submat_local(:,:), projmat_local(:,:), vec_subset_local(:,:), tmp_local(:,:), work_local(:) + + ! Initialize identity matrix + allocate(eye(max_nb, max_nb)) + eye = 0.0_wp + do i = 1, max_nb + eye(i, i) = 1.0_wp + end do + + ndispl_final = ndispl0 + + ! Storage for eigenvectors computed in parallel + allocate(locev_store(max_nb, n)) + + done = .false. + + ! --- Open parallel region once --- + !$omp parallel default(none) & + !$omp shared(n, ndispl0, nblist, nbcounts, h0, displdir, max_nb, eye, locev_store, & + !$omp ev, coverage, done, ndispl_final, eps, eps2) & + !$omp private(j, p, q, k, nnb, nb_idx, loceigs, locind, info, idx, n_curr, & + !$omp norm_ev1, norm_ev2, v_norm, d_dot, locev, & + !$omp submat_local, projmat_local, vec_subset_local, tmp_local, work_local) + + allocate(submat_local(max_nb, max_nb)) + allocate(projmat_local(max_nb, n)) + allocate(vec_subset_local(max_nb, n)) + allocate(tmp_local(max_nb, max_nb)) + allocate(work_local(10*max_nb + 10*n)) + + ! --- Outer Loop: Generate new directions --- + do n_curr = ndispl0, n - 1 + if (done) exit + + !$omp single + ev = 0.0_wp + coverage = 0.0_wp + !$omp end single + + ! --- Parallel Phase: Compute local eigenvectors --- + + !$omp do schedule(runtime) + do j = 1, n + nnb = nbcounts(j) + nb_idx(:nnb) = nblist(j)%neighbors(:nnb) + + ! Skip if subspace saturated + if (nnb <= n_curr) cycle + + ! 1. Extract submatrix H0 (submat_p) + do p = 1, nnb + do q = 1, nnb + submat_local(q, p) = h0(nb_idx(q), nb_idx(p)) + end do + end do + + ! 2. Local Projection + ! Form matrix A = displdir[neighbors, 0:n_curr] + do p = 1, n_curr + do q = 1, nnb + vec_subset_local(q, p) = displdir(nb_idx(q), p) + end do + end do + + if (n_curr > 0) then + projmat_local(:nnb, :n_curr) = -orth(vec_subset_local(:nnb, :n_curr)) ! TODO: why minus? + call mctc_gemm(projmat_local(:nnb, :n_curr), projmat_local(:nnb, :n_curr), tmp_local(:nnb, :nnb), transb="t") + projmat_local(:nnb, :nnb) = eye(:nnb, :nnb) - tmp_local(:nnb, :nnb) + else + projmat_local(:nnb, :nnb) = eye(:nnb, :nnb) + end if + + ! submat_p = P * submat_p * P.T + call mctc_gemm(submat_local(:nnb, :nnb), projmat_local(:nnb, :nnb), tmp_local(:nnb, :nnb), transb="t") + call mctc_gemm(projmat_local(:nnb, :nnb), tmp_local(:nnb, :nnb), submat_local(:nnb, :nnb)) + + ! Symmetrize + submat_local(:nnb, :nnb) = 0.5_wp * (submat_local(:nnb, :nnb) + transpose(submat_local(:nnb, :nnb))) + + ! 3. Diagonalization + ! dsyev: computes eigenvalues and eigenvectors in ascending order + call dsyev('V', 'U', nnb, submat_local, max_nb, loceigs, work_local, 10*max_nb, info) + + ! Find the index of maximum eigenvalue (first occurrence for ties, like Python's argmax) + ! dsyev sorts ascending, so normally we'd take the last, but for ties we need first max + locind = maxloc(loceigs(1:nnb), dim=1) + + ! Store the eigenvector for the serial phase + locev_store(1:nnb, j) = submat_local(1:nnb, locind) + end do + !$omp end do + + ! --- Serial Phase: Sign fixing and accumulation --- + !$omp single + do j = 1, n + nnb = nbcounts(j) + nb_idx(:nnb) = nblist(j)%neighbors(:nnb) + + if (nnb <= n_curr) cycle + + ! Retrieve eigenvector + locev(1:nnb) = locev_store(1:nnb, j) + + ! 4. Patching / Phase fixing + ! Calculate norms for sign decision + norm_ev1 = 0.0_wp + norm_ev2 = 0.0_wp + do p = 1, nnb + idx = nb_idx(p) + norm_ev1 = norm_ev1 + ((coverage(idx)*ev(idx) + locev(p))/(coverage(idx)+1.0_wp))**2 + norm_ev2 = norm_ev2 + ((coverage(idx)*ev(idx) - locev(p))/(coverage(idx)+1.0_wp))**2 + end do + norm_ev1 = sqrt(norm_ev1) + norm_ev2 = sqrt(norm_ev2) + + ! Apply update + if (norm_ev1 > norm_ev2 + eps) then + do p = 1, nnb + idx = nb_idx(p) + ev(idx) = (coverage(idx)*ev(idx) + locev(p))/(coverage(idx)+1.0_wp) + end do + else if (norm_ev1 < norm_ev2 - eps) then + do p = 1, nnb + idx = nb_idx(p) + ev(idx) = (coverage(idx)*ev(idx) - locev(p))/(coverage(idx)+1.0_wp) + end do + else + ! Deterministic sign fix based on max element + locind = maxloc(abs(locev(1:nnb)), dim=1) + if (locev(locind) > 0.0_wp) then + do p = 1, nnb + idx = nb_idx(p) + ev(idx) = (coverage(idx)*ev(idx) + locev(p))/(coverage(idx)+1.0_wp) + end do + else + do p = 1, nnb + idx = nb_idx(p) + ev(idx) = (coverage(idx)*ev(idx) - locev(p))/(coverage(idx)+1.0_wp) + end do + end if + end if + + ! Update coverage + do p = 1, nnb + coverage(nb_idx(p)) = coverage(nb_idx(p)) + 1.0_wp + end do + end do ! End J loop (serial phase) + + ! Project out previous columns from global ev + do k = 1, n_curr + d_dot = mctc_dot(ev, displdir(:, k)) + ev = ev - d_dot * displdir(:, k) + end do + ! --- Check Norm --- + v_norm = norm2(ev) + + if (v_norm < eps2) then + done = .true. + else + ! Normalize and store + ev = ev / v_norm + displdir(:, n_curr + 1) = ev + ndispl_final = n_curr + 1 + end if + !$omp end single + end do + + deallocate(submat_local, projmat_local, vec_subset_local, tmp_local, work_local) + !$omp end parallel + + deallocate(eye, locev_store) +end subroutine gen_displdir + +!> Setup an orthonormal basis using SVD +function orth(A, tol_in) result(Q) + real(wp), intent(in) :: A(:,:) + real(wp), intent(in), optional :: tol_in + real(wp), allocatable :: Q(:,:) + + real(wp), allocatable :: Acopy(:,:), U(:,:), S(:), VT(:,:), work(:) + real(wp) :: tol + integer :: m, n, lwork, info, i, k, rk + + m = size(A, 1) + n = size(A, 2) + k = min(m, n) + + allocate(Acopy(m, n), U(m, k), S(k), VT(k, n), work(1)) + + Acopy = A + + call dgesvd('S', 'N', m, n, Acopy, m, S, U, m, VT, k, work, -1, info) + lwork = int(work(1)) + deallocate(work) + allocate(work(lwork)) + + call dgesvd('S', 'N', m, n, Acopy, m, S, U, m, VT, k, work, lwork, info) + + if (present(tol_in)) then + tol = tol_in + else + tol = max(m, n) * S(1) * epsilon(1.0_wp) + end if + + rk = 0 + do i = 1, k + if (S(i) > tol) rk = rk + 1 + end do + + allocate(Q(m, rk)) + Q = U(:, 1:rk) + + deallocate(Acopy, U, S, VT, work) +end function orth + +!> Calculates a modified Swart model Hessian +subroutine swart(env, xyz, at, hess_out) + !> Computation environment + type(TEnvironment), intent(inout) :: env + !> coords + real(wp), intent(in) :: xyz(:, :) + !> ordinal numbers + integer, intent(in) :: at(:) + !> the full model hessian + real(wp), intent(inout) :: hess_out(:, :) + + real(wp), parameter :: wthr = 0.3_wp, f = 0.12_wp, tolth = 0.2_wp, eps1 = wthr**2, eps2 = wthr**2 / exp(1.0_wp) + + real(wp) :: equildist, Hint, bmat6(6), bmat9(9), bmat29(2, 9), outer6(6, 6), outer9(9, 9), s_ijjk, costh, sinth, th1, scalelin + real(wp), allocatable :: screenfunc(:, :), hess_local(:, :) + real(wp) :: ri, rj + integer :: i, j, k, nat, N, i1, i2, j1, j2, k1, k2 + + nat = size(xyz, 2) + N = 3*nat + + hess_out = 0.0_wp + + allocate(screenfunc(nat, nat)) + do i = 1, nat + do j = i + 1, nat + ri = get_cov_rad(at(i)) + rj = get_cov_rad(at(j)) + if (ri < 0.0_wp .or. rj < 0.0_wp) then + call env%error("swart: covalent radii only defined for 1-103", source) + return + end if + + equildist = ri + rj + screenfunc(i, j) = exp(1.0_wp - norm2(xyz(:, i) - xyz(:, j)) / equildist) + screenfunc(j, i) = screenfunc(i, j) + end do + end do + + !$omp parallel default(none) & + !$omp shared(nat, N, xyz, screenfunc, hess_out) private(i, j, k) & + !$omp private(Hint, bmat6, bmat9, bmat29, outer6, outer9, s_ijjk, costh, sinth, th1, scalelin) & + !$omp private(i1, i2, j1, j2, k1, k2, hess_local) + allocate(hess_local(N, N)) + hess_local = 0.0_wp + + !$omp do schedule(runtime) + do i = 1, nat + do j = i + 1, nat + Hint = 0.35_wp * screenfunc(i, j)**3 + bmat6 = bmat_bond(xyz(:, i) - xyz(:, j)) + outer6 = (spread(bmat6, dim=2, ncopies=6) * spread(bmat6, dim=1, ncopies=6)) + i1 = 3 * i - 2 + i2 = 3 * i + j1 = 3 * j - 2 + j2 = 3 * j + hess_local(i1:i2, i1:i2) = hess_local(i1:i2, i1:i2) + Hint * outer6(1:3, 1:3) + hess_local(i1:i2, j1:j2) = hess_local(i1:i2, j1:j2) + Hint * outer6(1:3, 4:6) + hess_local(j1:j2, i1:i2) = hess_local(j1:j2, i1:i2) + Hint * outer6(4:6, 1:3) + hess_local(j1:j2, j1:j2) = hess_local(j1:j2, j1:j2) + Hint * outer6(4:6, 4:6) + end do + end do + !$omp end do + + !$omp do schedule(runtime) + do i = 1, nat + do j = 1, nat + if (i == j) cycle + if (screenfunc(i, j) < eps2) cycle + do k = i + 1, nat + if (k == j) cycle + s_ijjk = screenfunc(i, j) * screenfunc(j, k) + if (s_ijjk < eps1) cycle + + costh = cosangle(xyz(:, i) - xyz(:, j), xyz(:, k) - xyz(:, j)) + sinth = sqrt(max(0.0_wp, 1.0_wp - costh**2)) + Hint = 0.075_wp * s_ijjk**2 * (f + (1 - f) * sinth)**2 + bmat9 = bmat_angle(xyz(:, i) - xyz(:, j), xyz(:, k) - xyz(:, j)) + + if (costh > 1.0_wp - tolth) then + th1 = 1.0_wp - costh + else + th1 = 1.0_wp + costh + end if + + i1 = 3 * i - 2 + i2 = 3 * i + j1 = 3 * j - 2 + j2 = 3 * j + k1 = 3 * k - 2 + k2 = 3 * k + if (th1 < tolth) then + scalelin = (1.0_wp - (th1 / tolth)**2)**2 + if (costh > 1.0_wp - tolth) then + bmat29 = bmat_linangle(xyz(:, i) - xyz(:, j), xyz(:, k) - xyz(:, j)) + bmat9 = scalelin * bmat29(1, :) + (1.0_wp - scalelin) * bmat9 + outer9 = Hint * spread(bmat29(2, :), dim=2, ncopies=9) * spread(bmat29(2, :), dim=1, ncopies=9) + hess_local(i1:i2, i1:i2) = hess_local(i1:i2, i1:i2) + outer9(1:3, 1:3) + hess_local(i1:i2, j1:j2) = hess_local(i1:i2, j1:j2) + outer9(1:3, 4:6) + hess_local(i1:i2, k1:k2) = hess_local(i1:i2, k1:k2) + outer9(1:3, 7:9) + hess_local(j1:j2, i1:i2) = hess_local(j1:j2, i1:i2) + outer9(4:6, 1:3) + hess_local(j1:j2, j1:j2) = hess_local(j1:j2, j1:j2) + outer9(4:6, 4:6) + hess_local(j1:j2, k1:k2) = hess_local(j1:j2, k1:k2) + outer9(4:6, 7:9) + hess_local(k1:k2, i1:i2) = hess_local(k1:k2, i1:i2) + outer9(7:9, 1:3) + hess_local(k1:k2, j1:j2) = hess_local(k1:k2, j1:j2) + outer9(7:9, 4:6) + hess_local(k1:k2, k1:k2) = hess_local(k1:k2, k1:k2) + outer9(7:9, 7:9) + else + bmat9 = (1.0_wp - scalelin) * bmat9 + end if + end if + + outer9 = Hint * spread(bmat9, dim=2, ncopies=9) * spread(bmat9, dim=1, ncopies=9) + hess_local(i1:i2, i1:i2) = hess_local(i1:i2, i1:i2) + outer9(1:3, 1:3) + hess_local(i1:i2, j1:j2) = hess_local(i1:i2, j1:j2) + outer9(1:3, 4:6) + hess_local(i1:i2, k1:k2) = hess_local(i1:i2, k1:k2) + outer9(1:3, 7:9) + hess_local(j1:j2, i1:i2) = hess_local(j1:j2, i1:i2) + outer9(4:6, 1:3) + hess_local(j1:j2, j1:j2) = hess_local(j1:j2, j1:j2) + outer9(4:6, 4:6) + hess_local(j1:j2, k1:k2) = hess_local(j1:j2, k1:k2) + outer9(4:6, 7:9) + hess_local(k1:k2, i1:i2) = hess_local(k1:k2, i1:i2) + outer9(7:9, 1:3) + hess_local(k1:k2, j1:j2) = hess_local(k1:k2, j1:j2) + outer9(7:9, 4:6) + hess_local(k1:k2, k1:k2) = hess_local(k1:k2, k1:k2) + outer9(7:9, 7:9) + end do + end do + end do + !$omp end do + + !$omp critical (swart_hess_merge) + hess_out(:, :) = hess_out + hess_local + !$omp end critical (swart_hess_merge) + deallocate(hess_local) + !$omp end parallel +end subroutine swart + +!> Wilson B matrix for bonds +function bmat_bond(vec) result(bmat) + real(wp), intent(in) :: vec(3) + + real(wp) :: l, bmat(6) + + bmat = 0.0_wp + l = norm2(vec) + + bmat(1:3) = vec(:) / l + bmat(4:6) = -vec(:) / l +end function bmat_bond + +!> Wilson B matrix for non-linear angles +function bmat_angle(vec1, vec2) result(bmat) + real(wp), intent(in) :: vec1(3), vec2(3) + real(wp) :: bmat(9) + real(wp) :: l1, l2, nvec1(3), nvec2(3) + real(wp) :: dl(2, 6), dnvec(2, 3, 6), dinprod(9) + real(wp) :: dot_n1n2 + integer :: ii + + l1 = norm2(vec1) + l2 = norm2(vec2) + nvec1 = vec1 / l1 + nvec2 = vec2 / l2 + + dl = 0.0_wp + dl(1, 1:3) = nvec1 + dl(1, 4:6) = -nvec1 + dl(2, 1:3) = nvec2 + dl(2, 4:6) = -nvec2 + + dnvec = 0.0_wp + do ii = 1, 6 + dnvec(1, 1:3, ii) = -nvec1 * dl(1, ii) / l1 + dnvec(2, 1:3, ii) = -nvec2 * dl(2, ii) / l2 + end do + do ii = 1, 3 + dnvec(1, ii, ii) = dnvec(1, ii, ii) + 1.0_wp/l1 + dnvec(2, ii, ii) = dnvec(2, ii, ii) + 1.0_wp/l2 + dnvec(1, ii, ii+3) = dnvec(1, ii, ii+3) - 1.0_wp/l1 + dnvec(2, ii, ii+3) = dnvec(2, ii, ii+3) - 1.0_wp/l2 + end do + + dinprod = 0.0_wp + do ii = 1, 3 + dinprod(ii) = mctc_dot(dnvec(1, :, ii), nvec2) + dinprod(ii+3) = mctc_dot(dnvec(1, :, ii+3), nvec2) + mctc_dot(dnvec(2, :, ii+3), nvec1) + dinprod(ii+6) = mctc_dot(dnvec(2, :, ii), nvec1) + end do + + dot_n1n2 = mctc_dot(nvec1, nvec2) + bmat = -dinprod / sqrt(max(1.0e-15_wp, 1.0_wp - dot_n1n2**2)) +end function bmat_angle + +!> Wirson B matrix for linear angles +function bmat_linangle(vec1, vec2) result(bmat) + real(wp), intent(in) :: vec1(3), vec2(3) + real(wp) :: bmat(2,9) + real(wp) :: l1, l2, nvec1(3), nvec2(3) + real(wp) :: vn(3), vn2(3), nvn + real(wp), parameter :: xaxis(3) = [1.0_wp, 0.0_wp, 0.0_wp], yaxis(3) = [0.0_wp, 1.0_wp, 0.0_wp] + + l1 = norm2(vec1) + l2 = norm2(vec2) + nvec1 = vec1 / l1 + nvec2 = vec2 / l2 + + vn(1) = vec1(2) * vec2(3) - vec1(3) * vec2(2) + vn(2) = vec1(3) * vec2(1) - vec1(1) * vec2(3) + vn(3) = vec1(1) * vec2(2) - vec1(2) * vec2(1) + nvn = norm2(vn) + + if (nvn < 1.0e-15_wp) then + vn = xaxis - mctc_dot(xaxis, vec1) / l1**2 * vec1 + nvn = norm2(vn) + if (nvn < 1.0e-15_wp) then + vn = yaxis - mctc_dot(yaxis, vec1) / l1**2 * vec1 + nvn = norm2(vn) + end if + end if + vn = vn / nvn + + vn2(1) = (vec1(2) - vec2(2)) * vn(3) - (vec1(3) - vec2(3)) * vn(2) + vn2(2) = (vec1(3) - vec2(3)) * vn(1) - (vec1(1) - vec2(1)) * vn(3) + vn2(3) = (vec1(1) - vec2(1)) * vn(2) - (vec1(2) - vec2(2)) * vn(1) + vn2 = vn2 / norm2(vn2) + + bmat = 0.0_wp + bmat(2, 1:3) = vn / l1 + bmat(2, 7:9) = vn / l2 + bmat(2, 4:6) = -bmat(2, 1:3) - bmat(2, 7:9) + bmat(1, 1:3) = vn2 / l1 + bmat(1, 7:9) = vn2 / l2 + bmat(1, 4:6) = -bmat(1, 1:3) - bmat(1, 7:9) +end function bmat_linangle + +!> cos(Angle) between two vectors +function cosangle(vec1, vec2) result(cos_theta) + implicit none + real(wp), intent(in) :: vec1(3), vec2(3) + real(wp) :: cos_theta + + cos_theta = mctc_dot(vec1, vec2) / (norm2(vec1) * norm2(vec2)) +end function cosangle +end module xtb_o1numhess diff --git a/src/param/CMakeLists.txt b/src/param/CMakeLists.txt index f1fd04c5f..de29135c7 100644 --- a/src/param/CMakeLists.txt +++ b/src/param/CMakeLists.txt @@ -23,6 +23,8 @@ list(APPEND srcs "${dir}/sqrtzr4r2.f90" "${dir}/vdwradd3.f90" "${dir}/vdwradcosmo.f90" + "${dir}/covalentrad.f90" + "${dir}/uffvdwrad.f90" ) set(srcs ${srcs} PARENT_SCOPE) diff --git a/src/param/covalentrad.f90 b/src/param/covalentrad.f90 new file mode 100644 index 000000000..512a9c828 --- /dev/null +++ b/src/param/covalentrad.f90 @@ -0,0 +1,56 @@ +! This file is part of xtb. +! +! Copyright (C) 2026-2027 Leopold M. Seidler +! +! xtb is free software: you can redistribute it and/or modify it under +! the terms of the GNU Lesser General Public License as published by +! the Free Software Foundation, either version 3 of the License, or +! (at your option) any later version. +! +! xtb is distributed in the hope that it will be useful, +! but WITHOUT ANY WARRANTY; without even the implied warranty of +! MERCHANTABILITY or FITNESS FOR A PARTICULAR PURPOSE. See the +! GNU Lesser General Public License for more details. +! +! You should have received a copy of the GNU Lesser General Public License +! along with xtb. If not, see . +! +!> Unmodified covalent radii from Pyykko and Atsumi, Chem. Eur. J. 15, 2009, +!> 188-197 +module xtb_param_covalentrad + use xtb_mctc_accuracy, only : wp + use xtb_mctc_convert, only : autoaa + implicit none + private + + public :: get_cov_rad + + !> covalent radii + real(wp), parameter :: cov(103) = [& + & 0.32_wp, 0.46_wp, 1.33_wp, 1.02_wp, 0.85_wp, 0.75_wp, 0.71_wp, 0.63_wp, 0.64_wp, 0.67_wp, & + & 1.55_wp, 1.39_wp, 1.26_wp, 1.16_wp, 1.11_wp, 1.03_wp, 0.99_wp, 0.96_wp, 1.96_wp, 1.71_wp, 1.48_wp, & + & 1.36_wp, 1.34_wp, 1.22_wp, 1.19_wp, 1.16_wp, 1.10_wp, 1.11_wp, 1.12_wp, 1.18_wp, 1.24_wp, 1.21_wp, & + & 1.21_wp, 1.16_wp, 1.14_wp, 1.17_wp, 2.10_wp, 1.85_wp, 1.63_wp, 1.54_wp, 1.47_wp, 1.38_wp, 1.28_wp, & + & 1.25_wp, 1.25_wp, 1.20_wp, 1.28_wp, 1.36_wp, 1.42_wp, 1.40_wp, 1.40_wp, 1.36_wp, 1.33_wp, 1.31_wp, & + & 2.32_wp, 1.96_wp, 1.80_wp, 1.63_wp, 1.76_wp, 1.74_wp, 1.73_wp, 1.72_wp, 1.68_wp, 1.69_wp, 1.68_wp, & + & 1.67_wp, 1.66_wp, 1.65_wp, 1.64_wp, 1.70_wp, 1.62_wp, 1.52_wp, 1.46_wp, 1.37_wp, 1.31_wp, 1.29_wp, & + & 1.22_wp, 1.23_wp, 1.24_wp, 1.33_wp, 1.44_wp, 1.44_wp, 1.51_wp, 1.45_wp, 1.47_wp, 1.42_wp, 2.23_wp, & + & 2.01_wp, 1.86_wp, 1.75_wp, 1.69_wp, 1.70_wp, 1.71_wp, 1.72_wp, 1.66_wp, 1.66_wp, 1.68_wp, 1.68_wp, & + & 1.65_wp, 1.67_wp, 1.73_wp, 1.76_wp, 1.61_wp] / autoaa + + ! NOTE: these should later be moved to mctc-lib + contains + +function get_cov_rad(at) result(rad) + integer, intent(in) :: at + + real(wp) :: rad + + if (at > 103 .or. at < 1) then + rad = -1.0_wp + else + rad = cov(at) + end if + +end function get_cov_rad +end module xtb_param_covalentrad diff --git a/src/param/meson.build b/src/param/meson.build index dca770ca6..7a5bde22c 100644 --- a/src/param/meson.build +++ b/src/param/meson.build @@ -21,4 +21,6 @@ srcs += files( 'sqrtzr4r2.f90', 'vdwradd3.f90', 'vdwradcosmo.f90', + 'covalentrad.f90', + 'uffvdwrad.f90', ) diff --git a/src/param/uffvdwrad.f90 b/src/param/uffvdwrad.f90 new file mode 100644 index 000000000..89be73126 --- /dev/null +++ b/src/param/uffvdwrad.f90 @@ -0,0 +1,54 @@ +! This file is part of xtb. +! +! Copyright (C) 2026-2027 Leopold M. Seidler +! +! xtb is free software: you can redistribute it and/or modify it under +! the terms of the GNU Lesser General Public License as published by +! the Free Software Foundation, either version 3 of the License, or +! (at your option) any later version. +! +! xtb is distributed in the hope that it will be useful, +! but WITHOUT ANY WARRANTY; without even the implied warranty of +! MERCHANTABILITY or FITNESS FOR A PARTICULAR PURPOSE. See the +! GNU Lesser General Public License for more details. +! +! You should have received a copy of the GNU Lesser General Public License +! along with xtb. If not, see . +!> UFF vdw radii - could be replaced with any other vdw radii i guess +module xtb_param_uffvdwrad + use xtb_mctc_accuracy, only : wp + use xtb_mctc_convert, only : autoaa + implicit none + private + + public :: get_rad + + real(wp), parameter :: vdw_radii(103) = [ & + 2.886_wp, 2.362_wp, 2.451_wp, 2.745_wp, 4.083_wp, 3.851_wp, 3.66_wp, 3.5_wp, 3.364_wp, & + 3.243_wp, 2.983_wp, 3.021_wp, 4.499_wp, 4.295_wp, 4.147_wp, 4.035_wp, 3.947_wp, 3.868_wp, & + 3.812_wp, 3.399_wp, 3.295_wp, 3.175_wp, 3.144_wp, 3.023_wp, 2.961_wp, 2.912_wp, 2.872_wp, & + 2.834_wp, 3.495_wp, 2.763_wp, 4.383_wp, 4.28_wp, 4.23_wp, 4.205_wp, 4.189_wp, 4.141_wp, & + 4.114_wp, 3.641_wp, 3.345_wp, 3.124_wp, 3.165_wp, 3.052_wp, 2.998_wp, 2.963_wp, 2.929_wp, & + 2.899_wp, 3.148_wp, 2.848_wp, 4.463_wp, 4.392_wp, 4.42_wp, 4.47_wp, 4.5_wp, 4.404_wp, & + 4.517_wp, 3.703_wp, 3.522_wp, 3.556_wp, 3.606_wp, 3.575_wp, 3.547_wp, 3.52_wp, 3.493_wp, & + 3.368_wp, 3.451_wp, 3.428_wp, 3.409_wp, 3.391_wp, 3.374_wp, 3.355_wp, 3.64_wp, 3.141_wp, & + 3.17_wp, 3.069_wp, 2.954_wp, 3.12_wp, 2.84_wp, 2.754_wp, 3.293_wp, 2.705_wp, 4.347_wp, & + 4.297_wp, 4.37_wp, 4.709_wp, 4.75_wp, 4.765_wp, 4.9_wp, 3.677_wp, 3.478_wp, 3.396_wp, & + 3.424_wp, 3.395_wp, 3.424_wp, 3.424_wp, 3.381_wp, 3.326_wp, 3.339_wp, 3.313_wp, 3.299_wp, & + 3.286_wp, 3.274_wp, 3.248_wp, 3.236_wp] * 0.5_wp / autoaa + + contains + +function get_rad(at) result(rad) + integer, intent(in) :: at + + real(wp) :: rad + + if (at > 103 .or. at < 1) then + rad = -1.0_wp + else + rad = vdw_radii(at) + end if + +end function get_rad +end module xtb_param_uffvdwrad diff --git a/src/prog/main.F90 b/src/prog/main.F90 index 8939123d2..76dbe62f7 100644 --- a/src/prog/main.F90 +++ b/src/prog/main.F90 @@ -172,6 +172,8 @@ subroutine xtbMain(env, argParser) !! ------------------------------------------------------------------------ logical :: struc_conversion_done = .false. logical :: anyopt, anyhess + ! logical for checking whether ODLR approximation can be used + logical :: odlr_valid !! ======================================================================== ! debugging variables for numerical gradient @@ -241,7 +243,17 @@ subroutine xtbMain(env, argParser) !> If hessian (or ohess or bhess) is requested in combination with PTB, conduct GFN2-xTB + PTB hessian anyhess = (set%runtyp == p_run_hess) .or. (set%runtyp == p_run_ohess) .or. (set%runtyp == p_run_bhess) if (anyhess) then - if(set%mode_extrun == p_ext_ptb) then + ! O1NumHess only supports Hessian calculation, nothing else + odlr_valid = freezeset%n == 0 .and. set%mode_extrun /= p_ext_ptb + if (set%o1numhess) then + if (.not. odlr_valid) then + call env%error("O1NumHess does not support frozen atoms/PTB", source) + end if + call env%warning("O1NumHess does not support calculation of IR or Raman activities", source) + if (set%step_hess >= 0.0005_wp) then + call env%warning("Step size for O1NumHess can be chosen to be much smaller (recommended: 1.0e-6)", source) + end if + else if(set%mode_extrun == p_ext_ptb) then set%mode_extrun = p_ext_xtb set%ptbsetup%ptb_in_hessian = .true. call set_gfn(env, 'method', '2') @@ -408,6 +420,11 @@ subroutine xtbMain(env, argParser) call env%checkpoint("reading geometry input '"//fname//"' failed") end if + if (mol%n == 1 .and. set%o1numhess) then + call env%warning("O1NumHess not supported for single atoms. Using default semi-numerical Hessian.", source) + set%o1numhess = .false. + end if + ! ------------------------------------------------------------------------ !> initialize the global storage call init_fix(mol%n) @@ -535,6 +552,7 @@ subroutine xtbMain(env, argParser) end if !> check if someone is still using GFN3... + ! TODO: this is probably a bit outdated now if (set%gfn_method == 3) then call env%terminate('Wait for some months - for now, please use gfn_method=2!') end if @@ -1856,6 +1874,9 @@ subroutine parseArguments(env, args, inputFile, paramFile, lgrad, & call set_opt(env, 'optlevel', sec) end if + case ('--o1nh') + set%o1numhess = .true. + case ('--omd') call set_runtyp('omd') call set_opt(env, 'optlevel', '-1') diff --git a/src/setparam.f90 b/src/setparam.f90 index f88c9feeb..9b58d3bbc 100644 --- a/src/setparam.f90 +++ b/src/setparam.f90 @@ -343,6 +343,8 @@ module xtb_setparam real(wp) :: step_hess = 0.005_wp ! Scaling factor for the hessian elements real(wp) :: scale_hess = 1.0_wp + ! Use O1NumHess for Hessian + logical :: o1numhess = .false. ! switch on gbsa for solvent if second argument is a valid solvent name type(TSolvInput) :: solvInput diff --git a/src/type/calculator.f90 b/src/type/calculator.f90 index 602afa971..925cf7cf9 100644 --- a/src/type/calculator.f90 +++ b/src/type/calculator.f90 @@ -17,18 +17,24 @@ !> abstract calculator that hides implementation details from calling codes module xtb_type_calculator + use xtb_mctc_convert, only : autoaa + use xtb_mctc_math, only : crossProd use xtb_mctc_accuracy, only : wp + use xtb_mctc_blas, only : mctc_gemm, mctc_nrm2, mctc_dot use xtb_solv_model, only : TSolvModel use xtb_type_data, only : scc_results use xtb_type_environment, only : TEnvironment use xtb_type_molecule, only : TMolecule use xtb_type_restart, only : TRestart + use xtb_o1numhess, only : adj_list, gen_local_hessian, & + & lr_loop, gen_displdir, get_neighbor_list, swart + use xtb_param_uffvdwrad, only : get_rad + use xtb_param_covalentrad, only : get_cov_rad implicit none public :: TCalculator private - !> Base calculator type, abstract :: TCalculator @@ -45,6 +51,9 @@ module xtb_type_calculator !> Perform hessian calculation procedure :: hessian + !> Perform ODLR approximated numerical hessian + procedure :: odlrhessian + !> Write informative printout procedure(writeInfo), deferred :: writeInfo @@ -92,7 +101,6 @@ subroutine singlepoint(self, env, mol, chk, printlevel, restart, & end subroutine singlepoint - subroutine writeInfo(self, unit, mol) import :: TCalculator, TMolecule @@ -108,10 +116,8 @@ subroutine writeInfo(self, unit, mol) end subroutine writeInfo end interface - contains - !> Evaluate hessian by finite difference for all atoms subroutine hessian(self, env, mol0, chk0, list, step, hess, dipgrad, polgrad) character(len=*), parameter :: source = "hessian_numdiff_numdiff2" @@ -143,7 +149,7 @@ subroutine hessian(self, env, mol0, chk0, list, step, hess, dipgrad, polgrad) call timing(t0, w0) step2 = 0.5_wp / step - !$omp parallel if(self%threadsafe) default(none) & + !$omp parallel if (self%threadsafe) default(none) & !$omp shared(self, env, mol0, chk0, list, step, hess, dipgrad, polgrad, step2, t0, w0) & !$omp private(kat, iat, jat, jc, jj, ii, er, el, egap, gr, gl, sr, sl, dr, dl, alphar, alphal, & !$omp& t1, w1) @@ -155,7 +161,7 @@ subroutine hessian(self, env, mol0, chk0, list, step, hess, dipgrad, polgrad) do ic = 1, 3 iat = list(kat) - ii = 3*(iat - 1) + ic + ii = 3 * (iat - 1) + ic er = 0.0_wp el = 0.0_wp gr = 0.0_wp @@ -171,13 +177,13 @@ subroutine hessian(self, env, mol0, chk0, list, step, hess, dipgrad, polgrad) polgrad(4, ii) = (alphar(1, 3) - alphal(1, 3)) * step2 polgrad(5, ii) = (alphar(2, 3) - alphal(2, 3)) * step2 polgrad(6, ii) = (alphar(3, 3) - alphal(3, 3)) * step2 - endif + end if dipgrad(:, ii) = (dr - dl) * step2 do jat = 1, mol0%n do jc = 1, 3 - jj = 3*(jat - 1) + jc + jj = 3 * (jat - 1) + jc hess(jj, ii) = hess(jj, ii) & & + (gr(jc, jat) - gl(jc, jat)) * step2 end do @@ -186,12 +192,12 @@ subroutine hessian(self, env, mol0, chk0, list, step, hess, dipgrad, polgrad) if (kat == 3 .and. ic == 3) then !$omp critical(xtb_numdiff2) call timing(t1, w1) - write(*,'("estimated CPU time",F10.2," min")') & - & 0.3333333_wp*size(list)*(t1-t0)/60.0_wp - write(*,'("estimated wall time",F10.2," min")') & - & 0.3333333_wp*size(list)*(w1-w0)/60.0_wp + write(*, '("estimated CPU time",F10.2," min")') & + & 0.3333333_wp * size(list) * (t1 - t0) / 60.0_wp + write(*, '("estimated wall time",F10.2," min")') & + & 0.3333333_wp * size(list) * (w1 - w0) / 60.0_wp !$omp end critical(xtb_numdiff2) - endif + end if end do end do @@ -227,4 +233,306 @@ subroutine hessian_point(self, env, mol0, chk0, iat, ic, step, energy, gradient, end subroutine hessian_point +!> Implementation according to Wang et al. (https://doi.org/10.1021/acs.jctc.5c01354) +subroutine odlrhessian(self, env, mol0, chk0, step, hess, final_err) + character(len=*), parameter :: source = "hessian_odlr" + !> Single point calculator + class(TCalculator), intent(inout) :: self + !> Computation environment + type(TEnvironment), intent(inout) :: env + !> Molecular structure data + type(TMolecule), intent(in) :: mol0 + !> Restart data + type(TRestart), intent(in) :: chk0 + !> Step size for numerical differentiation + real(wp), intent(in) :: step + !> Array to add Hessian to + real(wp), intent(inout) :: hess(:, :) + !> Array for displacement directions + real(wp), allocatable :: displdir(:, :) + !> Final error after all steps + real(wp), intent(out) :: final_err + + real(wp), parameter :: dmax = 1.0_wp, eps = 1.0e-8_wp, eps2 = 1.0e-15_wp, imagthr = 1.0e-8_wp + real(wp), parameter :: identity3(3, 3) = reshape([1, 0, 0, 0, 1, 0, 0, 0, 1], shape(identity3)) + + type(TMolecule) :: mol + type(TRestart) :: chk + type(scc_results) :: res + type(adj_list), allocatable :: neighborlist(:) + real(wp), allocatable :: distmat(:, :), h0(:, :), tmp_grad(:, :), & + & g0(:), g(:, :), work(:), eigvec(:, :), eigval(:) + real(wp) :: energy, sigma(3, 3), egap, dist, barycenter(3), inertia(3), & + & ax(3, 3), cross(3), Imat0, displmax, vec(3), ri, rj + logical :: terminate_run + integer, allocatable :: nbcounts(:) + integer :: N, i, j, k, Ntr, info, lwork, ndispl_final, max_nb, ndispl0, nimg + + ! ========== INITIALIZATION ========== + N = 3 * mol0%n + + call mol%copy(mol0) + call chk%copy(chk0) + + ! hessian initial guess + allocate(h0(N, N)) + call swart(env, mol%xyz, mol%at, h0) + call env%check(terminate_run) + if (terminate_run) then + return + end if + + ! calculate unperturbed gradient + allocate(tmp_grad(3, mol0%n)) + call self%singlepoint(env, mol, chk, -1, .true., energy, tmp_grad, sigma, egap, res) + g0 = reshape(tmp_grad,[N]) + + ! setup effective distmat + allocate(distmat(N, N)) + do i = 1, mol0%n + do j = i, mol0%n + ! effective distmat + ri = get_cov_rad(mol0%at(i)) + rj = get_cov_rad(mol0%at(j)) + if (ri < 0.0_wp .or. rj < 0.0_wp) then + call env%error("odlrhessian: covalent radii only defined for 1-103", source) + return + end if + dist = mol0%dist(i, j) - get_rad(mol0%at(i)) - get_rad(mol0%at(j)) + distmat(3 * i - 2:3 * i, 3 * j - 2:3 * j) = dist + distmat(3 * j - 2:3 * j, 3 * i - 2:3 * i) = dist + end do + end do + + allocate(displdir(N, N)) + displdir = 0.0_wp + ! set up initial displdir with trans, rot, and totally symmetric vib mode first + ! translational displacements + Ntr = 3 + do i = 1, mol0%n + displdir(3 * i - 2, 1) = 1.0_wp / sqrt(real(mol0%n, wp)) + displdir(3 * i - 1, 2) = 1.0_wp / sqrt(real(mol0%n, wp)) + displdir(3 * i, 3) = 1.0_wp / sqrt(real(mol0%n, wp)) + end do + + ! calculate inertial moment and axes + barycenter = sum(mol0%xyz, dim=2) / real(mol0%n, wp) + Imat0 = 0.0_wp + do i = 1, mol0%n + vec = mol0%xyz(:, i) - barycenter(:) + Imat0 = Imat0 + mctc_dot(vec, vec) + end do + ax = Imat0 * identity3 + do i = 1, 3 + do j = 1, 3 + do k = 1, mol0%n + ax(i, j) = ax(i, j) - (mol0%xyz(i, k) - barycenter(i)) * (mol0%xyz(j, k) - barycenter(j)) + end do + end do + end do + + lwork = -1 + allocate(work(1)) + call dsyev('V', 'U', 3, ax, 3, inertia, work, lwork, info) + lwork = int(work(1)) + deallocate(work) + allocate(work(lwork)) + call dsyev('V', 'U', 3, ax, 3, inertia, work, lwork, info) + + ! rotational displacements + do i = 1, 3 + if (inertia(i) < 1e-4_wp) cycle ! skips one mode if linear + Ntr = Ntr + 1 + do j = 1, mol0%n + cross = crossProd(ax(:, i), mol0%xyz(:, j) - barycenter(:)) + displdir(3 * j - 2:3 * j, Ntr) = cross + end do + displdir(:, Ntr) = displdir(:, Ntr) / norm2(displdir(:, Ntr)) + end do + + ! totally symmetric vibrational displacement + do i = 1, mol0%n + displdir(3 * i - 2:3 * i, Ntr + 1) = mol0%xyz(:, i) - barycenter(:) + end do + displdir(:, Ntr + 1) = displdir(:, Ntr + 1) / norm2(displdir(:, Ntr + 1)) + + ! get gradient derivs along rot/vib displacements + ! gradients along translations are zero + allocate(g(N, N)) + g = 0.0_wp + call get_gradient_derivs(self, env, step, 3, Ntr, displdir, mol0, chk0, g0, .false., g) + + ! for vib mode we need double-sided derivative + call get_gradient_derivs(self, env, step, Ntr, Ntr+1, displdir, mol0, chk0, g0, .true., g) + + ! generate remaining displdirs based on distmat and dmax + ! compute neighbor list + call get_neighbor_list(distmat, dmax, neighborlist) + allocate(nbcounts(N)) + max_nb = 0 + do i = 1, N + nbcounts(i) = size(neighborlist(i)%neighbors) + if (nbcounts(i) > max_nb) max_nb = nbcounts(i) + end do + + ! populate displdir + ndispl0 = Ntr + 1 + call gen_displdir(N, ndispl0, h0, max_nb, neighborlist, nbcounts, eps, eps2, displdir, ndispl_final) + + ! ========== GRADIENT DERIVATIVES ========== + ! write(env%unit, '(A)') "Calculating gradient derivatives" + call get_gradient_derivs(self, env, step, ndispl0, ndispl_final, displdir, mol0, chk0, g0, .false., g) + + ! ========== FINAL HESSIAN ========== + ! construct hessian from local hessian and odlr correction + ! compute local hessian + call gen_local_hessian(env, ndispl_final, distmat, displdir, g, dmax, hess) + + ! compute low rank correction + call lr_loop(env, ndispl_final, g, hess, displdir, final_err) + + call env%check(terminate_run) + if (terminate_run) then + return + end if + + ! diagonalize + ! keep hess in case there are no imaginary frequencies + allocate(eigvec(N, N)) + eigvec = hess + allocate(eigval(N)) + lwork = -1 + deallocate(work) + allocate(work(1)) + call dsyev('V', 'U', N, eigvec, N, eigval, work, lwork, info) + lwork = int(work(1)) + deallocate(work) + allocate(work(lwork)) + call dsyev('V', 'U', N, eigvec, N, eigval, work, lwork, info) + + ! check for imaginary frequencies + nimg = count(eigval < -imagthr) + ! only get the most negative freqs if they're too many + if (ndispl_final + nimg > N) nimg = N - ndispl_final + + if (nimg > 0) then + ! rerun with imaginary displacements + displdir(:, ndispl_final + 1:ndispl_final + nimg) = eigvec(:, 1:nimg) + ndispl0 = ndispl_final + ndispl_final = ndispl_final + nimg + call get_gradient_derivs(self, env, step, ndispl0, ndispl_final, displdir, mol0, chk0, g0, .false., g) + call gen_local_hessian(env, ndispl_final, distmat, displdir, g, dmax, hess) + call lr_loop(env, ndispl_final, g, hess, displdir, final_err) + end if + +end subroutine odlrhessian + +subroutine get_gradient_derivs(self, env, step, ndispl0, ndispl_final, displdir, mol0, chk0, g0, doublesided, g) + class(TCalculator), intent(inout) :: self + type(TEnvironment), intent(inout) :: env + real(wp), intent(in) :: step + integer, intent(in) :: ndispl0, ndispl_final + real(wp), intent(in) :: displdir(:, :) + type(TMolecule), intent(in) :: mol0 + type(TRestart), intent(in) :: chk0 + real(wp), intent(in) :: g0(:) + logical, intent(in) :: doublesided + real(wp), intent(inout) :: g(:, :) + + integer :: i, N + real(wp) :: displmax + + N = 3 * mol0%n + if (doublesided) then + !$omp parallel if (self%threadsafe) default(none) & + !$omp shared(self, env, mol0, chk0, step, g, N, ndispl0, ndispl_final, displdir) & + !$omp private(i, displmax) + !$omp do schedule(runtime) + do i = ndispl0 + 1, ndispl_final + displmax = maxval(abs(displdir(:, i))) + call gradient_derivs_doublesided_point(self, env, mol0, chk0, step, displdir(:, i), & + & displmax, N, g(:, i)) + end do + !$omp end parallel + else + !$omp parallel if (self%threadsafe) default(none) & + !$omp shared(self, env, mol0, chk0, step, g, N, ndispl0, ndispl_final, displdir, g0) & + !$omp private(i, displmax) + !$omp do schedule(runtime) + do i = ndispl0 + 1, ndispl_final + displmax = maxval(abs(displdir(:, i))) + call gradient_derivs_singlesided_point(self, env, mol0, chk0, step, displdir(:, i), & + & displmax, N, g0, g(:, i)) + end do + !$omp end parallel + end if +end subroutine get_gradient_derivs + +subroutine gradient_derivs_doublesided_point(self, env, mol0, chk0, step, displdir_i, & + & displmax, N, g_i) + class(TCalculator), intent(inout) :: self + type(TEnvironment), intent(inout) :: env + type(TMolecule), intent(in) :: mol0 + type(TRestart), intent(in) :: chk0 + real(wp), intent(in) :: step + real(wp), intent(in) :: displdir_i(:) + real(wp), intent(in) :: displmax + integer, intent(in) :: N + real(wp), intent(out) :: g_i(:) + + type(TMolecule) :: mol + type(TRestart) :: chk + type(scc_results) :: res + real(wp) :: sigma(3, 3), energy, egap + real(wp), allocatable :: tmp_gradl(:, :), tmp_gradr(:, :) + + allocate(tmp_gradr(3, mol0%n), tmp_gradl(3, mol0%n)) + tmp_gradl = 0.0_wp + tmp_gradr = 0.0_wp + + call mol%copy(mol0) + call chk%copy(chk0) + mol%xyz = mol0%xyz + reshape(step * displdir_i / displmax, [3, mol0%n]) + call self%singlepoint(env, mol, chk, -1, .true., energy, tmp_gradl, sigma, egap, res) + + call mol%copy(mol0) + call chk%copy(chk0) + mol%xyz = mol0%xyz - reshape(step * displdir_i / displmax, [3, mol0%n]) + call self%singlepoint(env, mol, chk, -1, .true., energy, tmp_gradr, sigma, egap, res) + + g_i = reshape(tmp_gradl - tmp_gradr, [N]) + g_i = g_i / step * displmax * 0.5_wp +end subroutine gradient_derivs_doublesided_point + +subroutine gradient_derivs_singlesided_point(self, env, mol0, chk0, step, displdir_i, & + & displmax, N, g0, g_i) + class(TCalculator), intent(inout) :: self + type(TEnvironment), intent(inout) :: env + type(TMolecule), intent(in) :: mol0 + type(TRestart), intent(in) :: chk0 + real(wp), intent(in) :: step + real(wp), intent(in) :: displdir_i(:) + real(wp), intent(in) :: displmax + integer, intent(in) :: N + real(wp), intent(in) :: g0(:) + real(wp), intent(out) :: g_i(:) + + type(TMolecule) :: mol + type(TRestart) :: chk + type(scc_results) :: res + real(wp) :: sigma(3, 3), energy, egap + real(wp), allocatable :: tmp_gradl(:, :) + + allocate(tmp_gradl(3, mol0%n)) + tmp_gradl = 0.0_wp + + call mol%copy(mol0) + call chk%copy(chk0) + mol%xyz = mol0%xyz + reshape(step * displdir_i / displmax, [3, mol0%n]) + call self%singlepoint(env, mol, chk, -1, .true., energy, tmp_gradl, sigma, egap, res) + + g_i = reshape(tmp_gradl, [N]) + g_i = (g_i - g0) / step * displmax +end subroutine gradient_derivs_singlesided_point + end module xtb_type_calculator diff --git a/src/xhelp.f90 b/src/xhelp.f90 index 1075bbc05..76a738052 100644 --- a/src/xhelp.f90 +++ b/src/xhelp.f90 @@ -83,12 +83,17 @@ subroutine citation(iunit) "* S. Grimme, M. Mueller, A. Hansen, J. Chem. Phys., 2023, 158, 124111.",& " DOI: 10.1063/5.0137838",& "",& + "for O1NumHess refer to:",& + "* B. Wang, S. Luo, Z. Wang, W. Liu,",& + " J. Chem. Theory Comput. 21, 10893-10909.",& + " DOI: 10.1021/acs.jctc.5c01354",& + "",& "with help from (in alphabetical order)",& "P. Atkinson, C. Bannwarth, F. Bohle, G. Brandenburg, E. Caldeweyher", & "M. Checinski, S. Dohm, S. Ehlert, S. Ehrlich, I. Gerasimov, C. Hölzer", & "A. Katbashev, J. Kohn, J. Koopman, C. Lavigne, S. Lehtola, F. März, M. Müller,", & "F. Musil, H. Neugebauer, J. Pisarek, C. Plett, P. Pracht, F. Pultar,", & - "J. Seibert, P. Shushkov, S. Spicher, M. Stahn, M. Steiner, T. Strunk,", & + "J. Seibert, L. M. Seidler, P. Shushkov, S. Spicher, M. Stahn, M. Steiner, T. Strunk,", & "J. Stückrath, T. Rose, and J. Unsleber", & "" end subroutine citation @@ -261,6 +266,9 @@ subroutine help(iunit) "--bhess [LEVEL]",& " perform a biased numerical hessian calculation on an ancopt(3) optimized geometry",& "",& + "--o1nh",& + " perform the numerical hessian calculation using the ODLR approximation (O1NumHess)",& + "",& "--md",& " molecular dynamics simulation on start geometry",& "",& diff --git a/test/unit/CMakeLists.txt b/test/unit/CMakeLists.txt index eacb75578..a30408a8a 100644 --- a/test/unit/CMakeLists.txt +++ b/test/unit/CMakeLists.txt @@ -92,7 +92,7 @@ foreach(t IN LISTS tests) set_tests_properties( "${PROJECT_NAME}/${t}" PROPERTIES - ENVIRONMENT XTBPATH=${PROJECT_SOURCE_DIR} + ENVIRONMENT "XTBPATH=${PROJECT_SOURCE_DIR};TEST_FIXTURES_DIR=${CMAKE_CURRENT_SOURCE_DIR}/fixtures" ) endforeach() # add PTB explicitly since it is not part of the tests list @@ -100,7 +100,7 @@ add_test("${PROJECT_NAME}/ptb" "${PROJECT_NAME}-tester" "ptb") set_tests_properties( "${PROJECT_NAME}/ptb" PROPERTIES - ENVIRONMENT XTBPATH=${PROJECT_SOURCE_DIR} + ENVIRONMENT "XTBPATH=${PROJECT_SOURCE_DIR};TEST_FIXTURES_DIR=${CMAKE_CURRENT_SOURCE_DIR}/fixtures" ) # xtb diff --git a/test/unit/fixtures/distmat_ref b/test/unit/fixtures/distmat_ref new file mode 100644 index 000000000..8d1dd3332 --- /dev/null +++ b/test/unit/fixtures/distmat_ref @@ -0,0 +1,8748 @@ +-6.61404096003, -6.61404096003, -6.61404096003, +-1.46873566362, -1.46873566362, -1.46873566362, +-3.08831493862, -3.08831493862, -3.08831493862, +-2.48036887068, -2.48036887068, -2.48036887068, + 2.98143453675, 2.98143453675, 2.98143453675, +-4.08317346454, -4.08317346454, -4.08317346454, +-4.54828270919, -4.54828270919, -4.54828270919, +-2.68080316130, -2.68080316130, -2.68080316130, +-2.40545689884, -2.40545689884, -2.40545689884, +-5.53043293098, -5.53043293098, -5.53043293098, +-0.85489112837, -0.85489112837, -0.85489112837, +-3.69553044633, -3.69553044633, -3.69553044633, +-4.16596221808, -4.16596221808, -4.16596221808, +-4.48537195162, 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a/test/unit/fixtures/nblist_ref b/test/unit/fixtures/nblist_ref new file mode 100644 index 000000000..0ae9c7acc --- /dev/null +++ b/test/unit/fixtures/nblist_ref @@ -0,0 +1,162 @@ +1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 70, 71, 72, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 127, 128, 129, 130, 131, 132, 136, 137, 138, 139, 140, 141, 142, 143, 144, 154, 155, 156, 157, 158, 159, 160, 161, 162 +1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 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27, 31, 32, 33, 34, 35, 36, 37, 38, 39, 43, 44, 45, 46, 47, 48, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 67, 68, 69, 70, 71, 72, 73, 74, 75, 79, 80, 81, 82, 83, 84, 85, 86, 87, 106, 107, 108, 109, 110, 111, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 145, 146, 147, 148, 149, 150, 151, 152, 153 +4, 5, 6, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 31, 32, 33, 34, 35, 36, 37, 38, 39, 43, 44, 45, 46, 47, 48, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 67, 68, 69, 70, 71, 72, 73, 74, 75, 79, 80, 81, 82, 83, 84, 85, 86, 87, 106, 107, 108, 109, 110, 111, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 145, 146, 147, 148, 149, 150, 151, 152, 153 +4, 5, 6, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 31, 32, 33, 34, 35, 36, 37, 38, 39, 43, 44, 45, 46, 47, 48, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 67, 68, 69, 70, 71, 72, 73, 74, 75, 79, 80, 81, 82, 83, 84, 85, 86, 87, 106, 107, 108, 109, 110, 111, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 145, 146, 147, 148, 149, 150, 151, 152, 153 +1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 58, 59, 60, 61, 62, 63, 64, 65, 66, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 112, 113, 114, 115, 116, 117, 118, 119, 120, 142, 143, 144, 154, 155, 156, 157, 158, 159, 160, 161, 162 +1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 58, 59, 60, 61, 62, 63, 64, 65, 66, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 112, 113, 114, 115, 116, 117, 118, 119, 120, 142, 143, 144, 154, 155, 156, 157, 158, 159, 160, 161, 162 +1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 58, 59, 60, 61, 62, 63, 64, 65, 66, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 112, 113, 114, 115, 116, 117, 118, 119, 120, 142, 143, 144, 154, 155, 156, 157, 158, 159, 160, 161, 162 +1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 34, 35, 36, 37, 38, 39, 40, 41, 42, 46, 47, 48, 49, 50, 51, 64, 65, 66, 76, 77, 78, 79, 80, 81, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 112, 113, 114, 115, 116, 117, 118, 119, 120, 142, 143, 144, 154, 155, 156, 157, 158, 159, 160, 161, 162 +1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 34, 35, 36, 37, 38, 39, 40, 41, 42, 46, 47, 48, 49, 50, 51, 64, 65, 66, 76, 77, 78, 79, 80, 81, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 112, 113, 114, 115, 116, 117, 118, 119, 120, 142, 143, 144, 154, 155, 156, 157, 158, 159, 160, 161, 162 +1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 34, 35, 36, 37, 38, 39, 40, 41, 42, 46, 47, 48, 49, 50, 51, 64, 65, 66, 76, 77, 78, 79, 80, 81, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 112, 113, 114, 115, 116, 117, 118, 119, 120, 142, 143, 144, 154, 155, 156, 157, 158, 159, 160, 161, 162 +1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 16, 17, 18, 19, 20, 21, 22, 23, 24, 28, 29, 30, 34, 35, 36, 37, 38, 39, 40, 41, 42, 46, 47, 48, 49, 50, 51, 64, 65, 66, 76, 77, 78, 79, 80, 81, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 112, 113, 114, 115, 116, 117, 118, 119, 120, 142, 143, 144, 154, 155, 156, 157, 158, 159, 160, 161, 162 +1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 16, 17, 18, 19, 20, 21, 22, 23, 24, 28, 29, 30, 34, 35, 36, 37, 38, 39, 40, 41, 42, 46, 47, 48, 49, 50, 51, 64, 65, 66, 76, 77, 78, 79, 80, 81, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 112, 113, 114, 115, 116, 117, 118, 119, 120, 142, 143, 144, 154, 155, 156, 157, 158, 159, 160, 161, 162 +1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 16, 17, 18, 19, 20, 21, 22, 23, 24, 28, 29, 30, 34, 35, 36, 37, 38, 39, 40, 41, 42, 46, 47, 48, 49, 50, 51, 64, 65, 66, 76, 77, 78, 79, 80, 81, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 112, 113, 114, 115, 116, 117, 118, 119, 120, 142, 143, 144, 154, 155, 156, 157, 158, 159, 160, 161, 162 diff --git a/test/unit/meson.build b/test/unit/meson.build index 32d23ebfd..bee72c6aa 100644 --- a/test/unit/meson.build +++ b/test/unit/meson.build @@ -81,6 +81,9 @@ tester = executable( link_language: 'fortran', ) +# Define fixtures directory environment variable +xtbenv.set('TEST_FIXTURES_DIR', meson.current_source_dir() / 'fixtures') + foreach t : tests test(t, tester, args: t, suite: 'unit', env: xtbenv) endforeach diff --git a/test/unit/test_hessian.f90 b/test/unit/test_hessian.f90 index 0af3acd76..b288c3674 100644 --- a/test/unit/test_hessian.f90 +++ b/test/unit/test_hessian.f90 @@ -19,6 +19,7 @@ module test_hessian use testdrive, only : new_unittest, unittest_type, error_type, check, test_failed use xtb_mctc_accuracy, only : wp use xtb_mctc_io, only : stdout + use xtb_mctc_convert, only : autoaa use xtb_type_options use xtb_type_molecule use xtb_type_restart @@ -28,6 +29,9 @@ module test_hessian use xtb_xtb_calculator, only : TxTBCalculator use xtb_main_setup, only : newXTBCalculator, newWavefunction + use xtb_modelhessian, only : mh_swart + use xtb_type_setvar, only : modhess_setvar + use xtb_o1numhess, only : gen_displdir, get_neighbor_list, adj_list, gen_local_hessian, lr_loop, swart implicit none private @@ -36,14 +40,41 @@ module test_hessian contains +function get_fixture_path(filename) result(fullpath) + character(len=*), intent(in) :: filename + character(len=:), allocatable :: fullpath + character(len=1024) :: base_dir + integer :: length, stat + + ! Get variable; status 0 means it exists + call get_environment_variable("TEST_FIXTURES_DIR", base_dir, length, stat) + + if (stat == 0) then + ! We effectively perform: "path/to/dir" // "/" // "file.txt" + ! On Windows this creates: "C:/path/to/dir/file.txt" (Valid) + ! On Linux this creates: "/path/to/dir/file.txt" (Valid) + fullpath = trim(base_dir) // '/' // filename + else + ! Fallback for manual running (assumes running from build dir or similar) + fullpath = "../test/unit/fixtures/" // filename + end if +end function get_fixture_path + !> Collect all exported unit tests subroutine collect_hessian(testsuite) !> Collection of tests type(unittest_type), allocatable, intent(out) :: testsuite(:) testsuite = [ & - new_unittest("gfn1", test_gfn1_hessian), & - new_unittest("gfn2", test_gfn2_hessian) & + new_unittest("gfn1_hessian", test_gfn1_hessian), & + new_unittest("gfn2_hessian", test_gfn2_hessian), & + new_unittest("nblist_o1numhess", test_nblist_o1numhess), & + new_unittest("modified_swart", test_modified_swart), & + new_unittest("o1numhess_gen_displdir", test_gendispldir_o1numhess), & + new_unittest("gfn1_o1numhess", test_o1numhess_gfn1), & + new_unittest("gfn2_o1numhess", test_o1numhess_gfn2), & + new_unittest("linear_h2o_gfn1_o1numhess", test_o1numhess_linear_h2o_gfn1), & + new_unittest("linear_h2o_gfn2_o1numhess", test_o1numhess_linear_h2o_gfn2) & ] end subroutine collect_hessian @@ -241,4 +272,1008 @@ subroutine test_gfn2_hessian(error) end subroutine test_gfn2_hessian +subroutine test_nblist_o1numhess(error) + type(error_type), allocatable, intent(out) :: error + integer, parameter :: nat = 54 + real(wp), parameter :: thr = 1.0e-4_wp + character(len=*), parameter :: sym(nat) = ['O', 'O', 'O', 'O', 'O', 'C', 'C', 'C', 'C', 'C', 'C', 'C', 'C', 'C', 'C', 'C', 'C', 'C', 'C', 'C', 'C', 'C', 'C', 'C', 'C', 'C', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H', 'H'] + integer, parameter :: at(nat) = [8, 8, 8, 8, 8, 6, 6, 6, 6, 6, 6, 6, 6, 6, 6, 6, 6, 6, 6, 6, 6, 6, 6, 6, 6, 6, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1] + real(wp), parameter :: xyz(3, nat) = reshape([ & + &-3.06876197244764_wp, 0.19448556443832_wp, -1.94335516402362_wp, & + & 0.48672317087736_wp, -2.37414977416329_wp, 0.74640403964754_wp, & + &-5.01392286848523_wp, 0.06500518477614_wp, 0.99438680911247_wp, & + &-5.92926707825204_wp, -2.14964638902524_wp, -0.09679054786651_wp, & + & 6.46124291527335_wp, -0.36657109114947_wp, -0.97517530474911_wp, & + &-0.99293297479044_wp, 1.21448854000979_wp, -0.25678568019737_wp, & + &-1.88187467277990_wp, 0.02222909651218_wp, 0.13250075340634_wp, & + & 0.40066850753014_wp, 1.13354627833840_wp, 0.35239280297367_wp, & + & 1.06360061679260_wp, -0.18376426171793_wp, -0.10101865874150_wp, & + &-3.21584077209344_wp, 0.45371531410135_wp, -0.55983996021412_wp, & + & 2.50598996635889_wp, -0.36661297069103_wp, 0.44518293352787_wp, & + &-1.85548086158727_wp, 2.43127007566346_wp, 0.07859124220201_wp, & + &-1.24286384401417_wp, -1.24793995135794_wp, -0.42270418964592_wp, & + &-3.28684067393579_wp, 1.96830601326335_wp, -0.25245092803743_wp, & + & 1.26790003151346_wp, 2.30531243156587_wp, -0.10078672435379_wp, & + & 0.15407031860948_wp, -1.37873895338713_wp, 0.15531287229906_wp, & + &-2.07585892781203_wp, -0.14181953375097_wp, 1.63925566896310_wp, & + & 3.31294973541281_wp, 0.88258965214860_wp, 0.16968950515907_wp, & + & 2.66729325199697_wp, 2.19367639453615_wp, 0.49736188521583_wp, & + & 3.14556493096524_wp, -1.55982985828490_wp, -0.28809822699537_wp, & + & 2.51422839817214_wp, -0.60483849487020_wp, 1.96446208259101_wp, & + &-4.41921521111641_wp, -0.28742042420872_wp, 0.00085168234654_wp, & + & 4.65019175446183_wp, -1.65135422072961_wp, -0.07463306598685_wp, & + & 4.57013308085424_wp, 0.84147357516259_wp, -0.28491650710015_wp, & + & 5.34019312592334_wp, -0.38176061789806_wp, -0.51245960465392_wp, & + &-4.85468325039185_wp, -1.53235168144890_wp, -0.73618634233715_wp, & + &-0.88536000505000_wp, 1.17775196980949_wp, -1.34698146609481_wp, & + & 0.32451699483681_wp, 1.15980925138336_wp, 1.44214229435536_wp, & + & 1.14530302264227_wp, -0.12136956510912_wp, -1.19525159153613_wp, & + &-1.57456838689741_wp, 3.30265656519013_wp, -0.50994722436245_wp, & + &-1.76218625627092_wp, 2.69093642014312_wp, 1.13270257354206_wp, & + &-1.18927493326531_wp, -1.18835746298682_wp, -1.51046637912891_wp, & + &-1.80784940235908_wp, -2.13948164603414_wp, -0.14598752625224_wp, & + &-3.96611761537147_wp, 2.13411373620025_wp, 0.58290206904660_wp, & + &-3.68591892958296_wp, 2.49809302066445_wp, -1.11882955134477_wp, & + & 0.81387859146875_wp, 3.24645064346949_wp, 0.21243822059035_wp, & + & 1.33729877444188_wp, 2.31000542053058_wp, -1.19098039484345_wp, & + &-1.12118685681340_wp, -0.32162061906065_wp, 2.12639045628194_wp, & + &-2.54463670293864_wp, 0.72913296780967_wp, 2.08567527228266_wp, & + &-2.70911977624777_wp, -1.00248434251682_wp, 1.84262485728548_wp, & + & 2.59391711447919_wp, 2.27953745210943_wp, 1.58574891610354_wp, & + & 3.29343891115649_wp, 3.01461931811614_wp, 0.14480636755127_wp, & + & 2.95983104730468_wp, -1.45350131071300_wp, -1.36092075616257_wp, & + & 2.67353385789435_wp, -2.48394831537700_wp, 0.04336940312963_wp, & + & 3.53564571272084_wp, -0.60633642649981_wp, 2.33669404875740_wp, & + & 1.97081004589295_wp, 0.17618341572015_wp, 2.48911941746077_wp, & + & 2.05619026864024_wp, -1.56170278103109_wp, 2.19420595639869_wp, & + &-3.73057965515078_wp, 0.69737538781391_wp, -2.43068227224802_wp, & + & 5.06838675345177_wp, -2.49659445557115_wp, -0.62352909086624_wp, & + & 4.88048000733017_wp, -1.80335421693271_wp, 0.98284255140168_wp, & + & 5.10835341462563_wp, 1.76010665629942_wp, -0.47938272166668_wp, & + &-4.00084962479015_wp, -2.21956028206792_wp, -0.80500973828872_wp, & + &-5.13568412213777_wp, -1.26351703151787_wp, -1.76363779186583_wp, & + &-6.13475894704690_wp, -1.61304366767513_wp, 0.68825272793312_wp],& + & shape(xyz)) + real(wp), parameter :: vdw_radii(1:103) = [ & + 2.886_wp, 2.362_wp, 2.451_wp, 2.745_wp, 4.083_wp, 3.851_wp, 3.66_wp, 3.5_wp, 3.364_wp, & + 3.243_wp, 2.983_wp, 3.021_wp, 4.499_wp, 4.295_wp, 4.147_wp, 4.035_wp, 3.947_wp, 3.868_wp, & + 3.812_wp, 3.399_wp, 3.295_wp, 3.175_wp, 3.144_wp, 3.023_wp, 2.961_wp, 2.912_wp, 2.872_wp, & + 2.834_wp, 3.495_wp, 2.763_wp, 4.383_wp, 4.28_wp, 4.23_wp, 4.205_wp, 4.189_wp, 4.141_wp, & + 4.114_wp, 3.641_wp, 3.345_wp, 3.124_wp, 3.165_wp, 3.052_wp, 2.998_wp, 2.963_wp, 2.929_wp, & + 2.899_wp, 3.148_wp, 2.848_wp, 4.463_wp, 4.392_wp, 4.42_wp, 4.47_wp, 4.5_wp, 4.404_wp, & + 4.517_wp, 3.703_wp, 3.522_wp, 3.556_wp, 3.606_wp, 3.575_wp, 3.547_wp, 3.52_wp, 3.493_wp, & + 3.368_wp, 3.451_wp, 3.428_wp, 3.409_wp, 3.391_wp, 3.374_wp, 3.355_wp, 3.64_wp, 3.141_wp, & + 3.17_wp, 3.069_wp, 2.954_wp, 3.12_wp, 2.84_wp, 2.754_wp, 3.293_wp, 2.705_wp, 4.347_wp, & + 4.297_wp, 4.37_wp, 4.709_wp, 4.75_wp, 4.765_wp, 4.9_wp, 3.677_wp, 3.478_wp, 3.396_wp, & + 3.424_wp, 3.395_wp, 3.424_wp, 3.424_wp, 3.381_wp, 3.326_wp, 3.339_wp, 3.313_wp, 3.299_wp, & + 3.286_wp, 3.274_wp, 3.248_wp, 3.236_wp & + ] / 2.0_wp / autoaa + real(wp), allocatable :: distmat_ref(:,:) + real(wp), parameter :: dmax = 1.0_wp, eps = 1.0e-8_wp, eps2 = 1.0e-15_wp + + type(adj_list), allocatable :: nblist_ref(:), nblist(:) + real(wp), allocatable :: distmat(:, :) + real(wp) :: dist + integer :: N, i, j, iunit, nnb + character(len=2048) :: line + character(len=:), allocatable :: fixture_path + logical :: is_same + + N = 3 * nat + + ! Read neighbor list from fixture file + fixture_path = get_fixture_path("nblist_ref") + allocate(nblist_ref(N)) + open(newunit=iunit, file=fixture_path, status='old') + do i = 1, N + read(iunit, '(a)') line + ! Count commas to determine number of neighbors + nnb = 1 + do j = 1, len_trim(line) + if (line(j:j) == ',') nnb = nnb + 1 + end do + allocate(nblist_ref(i)%neighbors(nnb)) + read(line, *) nblist_ref(i)%neighbors + end do + close(iunit) + + ! Read distance matrix from fixture file + fixture_path = get_fixture_path("distmat_ref") + allocate(distmat_ref(N, N)) + open(newunit=iunit, file=fixture_path, status='old') + read(iunit, *) distmat_ref + close(iunit) + + allocate(distmat(N, N)) + distmat = 0.0_wp + do i = 1, nat + do j = i, nat + ! effective distmat + dist = norm2(xyz(:, i) - xyz(:, j)) - vdw_radii(at(i)) - vdw_radii(at(j)) + distmat(3 * i - 2:3 * i, 3 * j - 2:3 * j) = dist + distmat(3 * j - 2:3 * j, 3 * i - 2:3 * i) = dist + end do + end do + + call get_neighbor_list(distmat, dmax, nblist) + + if (any(abs(distmat - distmat_ref) > thr)) then + call test_failed(error, "Distance Matrix not matching") + print *, "--- Distance Matrix ---" + do i = 1, N + print '(*(F21.14))', distmat(i, :) + end do + + print *, "--- Ref. Distance Matrix ---" + do i = 1, N + print '(*(F21.14))', distmat_ref(i, :) + end do + end if + + is_same = .true. + do i = 1, N + ! 1. Check if allocation status matches (both allocated or both not) + if (allocated(nblist_ref(i)%neighbors) .neqv. allocated(nblist(i)%neighbors)) then + is_same = .false. + end if + + ! 2. If allocated, check size and values + if (allocated(nblist_ref(i)%neighbors)) then + + ! Check Size + if (size(nblist_ref(i)%neighbors) /= size(nblist(i)%neighbors)) then + is_same = .false. + end if + + ! Check Values using ALL() intrinsic + if (.not. all(nblist_ref(i)%neighbors == nblist(i)%neighbors)) then + is_same = .false. + end if + end if + end do + + if (.not. is_same) then + call test_failed(error, "Adjacency list not matching") + print *, "--- Adjacency List ---" + do i = 1, N + if (allocated(nblist(i)%neighbors)) then + ! Print the node index, then all neighbors on one line + print '("Node ", I2, ": ", *(I4))', i, nblist(i)%neighbors + else + print '("Node ", I2, ": ")', i + end if + end do + + print *, "--- Ref. Adjacency List ---" + do i = 1, N + if (allocated(nblist_ref(i)%neighbors)) then + ! Print the node index, then all neighbors on one line + print '("Node ", I2, ": ", *(I4))', i, nblist_ref(i)%neighbors + else + print '("Node ", I2, ": ")', i + end if + end do + end if + +end subroutine test_nblist_o1numhess + +subroutine test_modified_swart(error) + type(error_type), allocatable, intent(out) :: error + integer, parameter :: nat = 3 + real(wp),parameter :: thr = 1.0e-7_wp + character(len=*), parameter :: sym(nat) = ["O", "H", "H"] + integer, parameter :: at(nat) = [8, 1, 1] + real(wp), parameter :: xyz(3, nat) = reshape([& + & 0.00000000000000_wp, 0.00000000034546_wp, 0.18900383618455_wp, & + & 0.00000000000000_wp, 1.45674735348811_wp, -0.88650486059828_wp, & + &-0.00000000000000_wp, -1.45674735383357_wp, -0.88650486086986_wp],& + & shape(xyz)) + ! swart model hessian from o1numhess utils + real(wp), parameter :: h0(9, 9) = reshape([& + & 1.1092305614e-03_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & + &-5.5461528244e-04_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & + &-5.5461527896e-04_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & + & 0.0000000000e+00_wp, 4.4184751144e-01_wp, -2.7552743027e-10_wp, & + & 0.0000000000e+00_wp, -2.2092375587e-01_wp, 1.6310770462e-01_wp, & + & 0.0000000000e+00_wp, -2.2092375557e-01_wp, -1.6310770435e-01_wp, & + & 0.0000000000e+00_wp, -2.7552743027e-10_wp, 2.9417034746e-01_wp, & + & 0.0000000000e+00_wp, 1.4319582461e-01_wp, -1.4708517387e-01_wp, & + & 0.0000000000e+00_wp, -1.4319582434e-01_wp, -1.4708517359e-01_wp, & + &-5.5461528244e-04_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & + & 1.6724709350e-03_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & + &-1.1178556526e-03_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & + & 0.0000000000e+00_wp, -2.2092375587e-01_wp, 1.4319582461e-01_wp, & + & 0.0000000000e+00_wp, 2.3323207511e-01_wp, -1.5315176462e-01_wp, & + & 0.0000000000e+00_wp, -1.2308319237e-02_wp, 9.9559400089e-03_wp, & + & 0.0000000000e+00_wp, 1.6310770462e-01_wp, -1.4708517387e-01_wp, & + & 0.0000000000e+00_wp, -1.5315176462e-01_wp, 1.3375368579e-01_wp, & + & 0.0000000000e+00_wp, -9.9559400048e-03_wp, 1.3331488088e-02_wp, & + &-5.5461527896e-04_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & + &-1.1178556526e-03_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & + & 1.6724709315e-03_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & + & 0.0000000000e+00_wp, -2.2092375557e-01_wp, -1.4319582434e-01_wp, & + & 0.0000000000e+00_wp, -1.2308319237e-02_wp, -9.9559400048e-03_wp, & + & 0.0000000000e+00_wp, 2.3323207480e-01_wp, 1.5315176434e-01_wp, & + & 0.0000000000e+00_wp, -1.6310770435e-01_wp, -1.4708517359e-01_wp, & + & 0.0000000000e+00_wp, 9.9559400089e-03_wp, 1.3331488088e-02_wp, & + & 0.0000000000e+00_wp, 1.5315176434e-01_wp, 1.3375368550e-01_wp],& + & shape(h0)) + + type(TEnvironment) :: env + integer :: i + real(wp), allocatable :: hess_out(:, :) + + call init(env) + + allocate(hess_out(3*nat, 3*nat)) + hess_out = 0.0_wp + call swart(env, xyz, at, hess_out) + + if (any(abs(hess_out - h0) > thr)) then + call test_failed(error, "Hessians do not match") + + print *, "--- hessian ---" + do i = 1, 3*nat + print '(*(F21.14))', hess_out(i, :) + end do + + print *, "--- Ref. hessian ---" + do i = 1, 3*nat + print '(*(F21.14))', h0(i, :) + end do + end if +end subroutine test_modified_swart + +subroutine test_gendispldir_o1numhess(error) + type(error_type), allocatable, intent(out) :: error + integer, parameter :: nat = 3 + real(wp),parameter :: thr = 1.0e-7_wp + character(len=*), parameter :: sym(nat) = ["O", "H", "H"] + real(wp), parameter :: xyz(3, nat) = reshape([& + & 0.00000000000000_wp, 0.00000000034546_wp, 0.18900383618455_wp, & + & 0.00000000000000_wp, 1.45674735348811_wp, -0.88650486059828_wp, & + &-0.00000000000000_wp, -1.45674735383357_wp, -0.88650486086986_wp],& + & shape(xyz)) + ! swart model hessian from o1numhess utils + real(wp), parameter :: h0(9, 9) = reshape([& + & 1.1092305614e-03_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & + &-5.5461528244e-04_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & + &-5.5461527896e-04_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & + & 0.0000000000e+00_wp, 4.4184751144e-01_wp, -2.7552743027e-10_wp, & + & 0.0000000000e+00_wp, -2.2092375587e-01_wp, 1.6310770462e-01_wp, & + & 0.0000000000e+00_wp, -2.2092375557e-01_wp, -1.6310770435e-01_wp, & + & 0.0000000000e+00_wp, -2.7552743027e-10_wp, 2.9417034746e-01_wp, & + & 0.0000000000e+00_wp, 1.4319582461e-01_wp, -1.4708517387e-01_wp, & + & 0.0000000000e+00_wp, -1.4319582434e-01_wp, -1.4708517359e-01_wp, & + &-5.5461528244e-04_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & + & 1.6724709350e-03_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & + &-1.1178556526e-03_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & + & 0.0000000000e+00_wp, -2.2092375587e-01_wp, 1.4319582461e-01_wp, & + & 0.0000000000e+00_wp, 2.3323207511e-01_wp, -1.5315176462e-01_wp, & + & 0.0000000000e+00_wp, -1.2308319237e-02_wp, 9.9559400089e-03_wp, & + & 0.0000000000e+00_wp, 1.6310770462e-01_wp, -1.4708517387e-01_wp, & + & 0.0000000000e+00_wp, -1.5315176462e-01_wp, 1.3375368579e-01_wp, & + & 0.0000000000e+00_wp, -9.9559400048e-03_wp, 1.3331488088e-02_wp, & + &-5.5461527896e-04_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & + &-1.1178556526e-03_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & + & 1.6724709315e-03_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & + & 0.0000000000e+00_wp, -2.2092375557e-01_wp, -1.4319582434e-01_wp, & + & 0.0000000000e+00_wp, -1.2308319237e-02_wp, -9.9559400048e-03_wp, & + & 0.0000000000e+00_wp, 2.3323207480e-01_wp, 1.5315176434e-01_wp, & + & 0.0000000000e+00_wp, -1.6310770435e-01_wp, -1.4708517359e-01_wp, & + & 0.0000000000e+00_wp, 9.9559400089e-03_wp, 1.3331488088e-02_wp, & + & 0.0000000000e+00_wp, 1.5315176434e-01_wp, 1.3375368550e-01_wp],& + & shape(h0)) + ! Ref from o1numhess python implementation using the above h0 + real(wp), parameter :: displdir_ref(9, 3) = reshape([& + & 0.00000000000000000e+00_wp, 5.85920171106577004e-01_wp, 1.51794937958024002e-01_wp, & + & 0.00000000000000000e+00_wp, 4.38891753068939995e-01_wp, -2.48878406404109010e-01_wp, & + & 0.00000000000000000e+00_wp, 5.10352159263066002e-01_wp, 3.44427193104884989e-01_wp, & + & 2.83390078813432008e-01_wp, -1.26365402678647992e-01_wp, 5.36139605082272009e-01_wp, & + & -2.09750793632672975e-17_wp, -2.71810289210553018e-01_wp, -4.85072467210535029e-01_wp, & + & 4.19501587265346009e-17_wp, -3.21710376864937989e-01_wp, 4.51223308073935011e-01_wp, & + & 5.04407285834402014e-01_wp, 4.29600509606577008e-02_wp, -1.42605077919505999e-01_wp, & + & 5.98879533835269020e-01_wp, 2.40065553767858998e-02_wp, 4.97688397830703991e-02_wp, & + & 5.98879533835269020e-01_wp, 2.84749410320055008e-02_wp, -4.70536852490466000e-02_wp],& + & shape(displdir_ref)) + real(wp), parameter :: dmax = 1.0_wp, eps = 1.0e-8_wp, eps2 = 1.0e-15_wp + + type(adj_list), allocatable :: neighborlist(:) + real(wp), allocatable :: distmat(:, :), displdir(:, :) + integer, allocatable :: nbcounts(:) + integer :: i, j, N, max_nb, ndispl0, ndispl_final + + N = 3 * nat + + ! setup distmat + allocate(distmat(N, N)) + do i = 1, N + do j = 1, N + distmat(i, j) = abs(i - j) + end do + end do + + ! compute neighbor list + call get_neighbor_list(distmat, dmax, neighborlist) + allocate(nbcounts(N)) + max_nb = 0 + do i = 1, N + nbcounts(i) = size(neighborlist(i)%neighbors) + if (nbcounts(i) > max_nb) max_nb = nbcounts(i) + end do + + ! populate displdir + ndispl0 = 0 + allocate(displdir(N, N)) + call gen_displdir(N, ndispl0, h0, max_nb, neighborlist, nbcounts, eps, eps2, displdir, ndispl_final) + + if (ndispl_final /= 3) then + call test_failed(error, "Number of displacements not matching") + print *, "ndispl_final: ", ndispl_final + end if + + if (any(abs(displdir_ref - displdir(:, :ndispl_final)) > thr)) then + call test_failed(error, "Displacements not matching") + print *, "--- displdir ---" + do i = 1, N + print '(*(F21.14))', displdir(i, :ndispl_final) + end do + + print *, "--- Ref. displdir ---" + do i = 1, N + print '(*(F21.14))', displdir_ref(i, :) + end do + end if + +end subroutine test_gendispldir_o1numhess + +subroutine test_o1numhess_gfn1(error) + type(error_type), allocatable, intent(out) :: error + integer, parameter :: nat = 3 + real(wp),parameter :: thr1 = 1.0e-9_wp, thr2 = 1.0e-5_wp + character(len=*), parameter :: sym(nat) = ["O", "H", "H"] + real(wp), parameter :: xyz(3, nat) = reshape([& + & 0.00000000000000_wp, 0.00000000034546_wp, 0.18900383618455_wp, & + & 0.00000000000000_wp, 1.45674735348811_wp, -0.88650486059828_wp, & + &-0.00000000000000_wp, -1.45674735383357_wp, -0.88650486086986_wp],& + & shape(xyz)) + real(wp), parameter :: hessian_ref(9, 9) = reshape([& + & 9.6427214452304158E-005_wp, 7.9724999781439290E-011_wp, -1.3840003654029018E-007_wp, & + &-4.8213460516503025E-005_wp, -6.7504265780829648E-008_wp, 6.9205909101946085E-008_wp, & + &-4.8213753935792019E-005_wp, 6.7417854867650525E-008_wp, 6.9189718349509533E-008_wp, & + & 7.9724999781439290E-011_wp, 0.65431356973123023_wp, -7.4720523570619281E-007_wp, & + & 4.4325798795663372E-011_wp, -0.32715720199319237_wp, 0.24150286357164832_wp, & + &-1.2405079857710117E-010_wp, -0.32715636773669671_wp, -0.24150211636497051_wp, & + &-1.3840003654029018E-007_wp, -7.4720523570619281E-007_wp, 0.39702315113905740_wp, & + & 3.6004504315957250E-008_wp, 0.19343120065992384_wp, -0.19851179291786120_wp, & + & 1.0239553222433293E-007_wp,- 0.19343045344911730_wp, -0.19851135822773272_wp, & + &-4.8213460516503025E-005_wp, 4.4325798795663372E-011_wp, 3.6004504315957250E-008_wp, & + & 4.4189538089979658E-005_wp, 1.9027949582154744E-009_wp, -1.8014006716533711E-008_wp, & + & 4.0239224265213695E-006_wp, -1.9457835743300046E-009_wp, -1.7987696743810155E-008_wp, & + &-6.7504265780829648E-008_wp, -0.32715720199319237_wp, 0.19343120065992384_wp, & + & 1.9027949582154744E-009_wp, 0.34874368456677368_wp, -0.21746695535952912_wp, & + & 6.5601470822614196E-008_wp, -2.1586482575562844E-002_wp, 2.4035754703519811E-002_wp, & + & 6.9205909101946085E-008_wp, 0.24150286357164832_wp, -0.19851179291786120_wp, & + &-1.8014006716533711E-008_wp, -0.21746695535952912_wp, 0.18842607949434392_wp, & + &-5.1191902385412367E-008_wp, -2.4035908212783213E-002_wp, 1.0085713431492066E-002_wp, & + &-4.8213753935792019E-005_wp, -1.2405079857710117E-010_wp, 1.0239553222433293E-007_wp, & + & 4.0239224265213695E-006_wp, 6.5601470822614196E-008_wp, -5.1191902385412367E-008_wp, & + & 4.4189831509263550E-005_wp, -6.5472071293320507E-008_wp, -5.1202021605699378E-008_wp, & + & 6.7417854867650525E-008_wp, -0.32715636773669671_wp, -0.19343045344911730_wp, & + &-1.9457835743300046E-009_wp, -2.1586482575562844E-002_wp, -2.4035908212783213E-002_wp, & + &-6.5472071293320507E-008_wp, 0.34874285031290009_wp, 0.21746636165654390_wp, & + & 6.9189718349509533E-008_wp, -0.24150211636497051_wp, -0.19851135822773272_wp, & + &-1.7987696743810155E-008_wp, 2.4035754703519811E-002_wp, 1.0085713431492066E-002_wp, & + &-5.1202021605699378E-008_wp, 0.21746636165654390_wp, 0.18842564479480242_wp], & + & shape(hessian_ref)) + real(wp), parameter :: final_err_ref = 2.01474475e-6_wp + real(wp), parameter :: step = 1.0e-6_wp + + type(TMolecule) :: mol + type(TRestart) :: chk + type(TEnvironment) :: env + type(TxTBCalculator) :: calc + real(wp), allocatable :: hessian(:, :) + real(wp) :: final_err + integer :: N, i + + N = 3 * nat + call init(env) + call init(mol, sym, xyz) + + call newXTBCalculator(env, mol, calc, method=1, accuracy=1.0e-8_wp) + call newWavefunction(env, mol, calc, chk) + + allocate(hessian(N, N)) + call calc%odlrhessian(env, mol, chk, step, hessian, final_err) + + if (any(abs(hessian - hessian_ref) > thr1)) then + call test_failed(error, "Final Hessians do not match") + + print *, "--- hessian ---" + do i = 1, N + print '(*(F21.14))', hessian(i, :) + end do + + print *, "--- Ref. hessian ---" + do i = 1, N + print '(*(F21.14))', hessian_ref(i, :) + end do + end if + + if (abs(final_err - final_err_ref) > thr2) then + call test_failed(error, "Final error does not match") + print *, "--- Final error ---" + print '(*(F21.14))', final_err + print *, "--- Ref. final error ---" + print '(*(F21.14))', final_err_ref + end if +end subroutine test_o1numhess_gfn1 + +subroutine test_o1numhess_gfn2(error) + type(error_type), allocatable, intent(out) :: error + integer, parameter :: nat = 3 + real(wp),parameter :: thr1 = 1.0e-9_wp, thr2 = 1.0e-5_wp + character(len=*), parameter :: sym(nat) = ["O", "H", "H"] + real(wp), parameter :: xyz(3, nat) = reshape([& + & 0.00000000000000_wp, 0.00000000034546_wp, 0.18900383618455_wp, & + & 0.00000000000000_wp, 1.45674735348811_wp, -0.88650486059828_wp, & + &-0.00000000000000_wp, -1.45674735383357_wp, -0.88650486086986_wp],& + & shape(xyz)) + real(wp), parameter :: hessian_ref(9, 9) = reshape([& + &-7.8530493188148887E-004_wp, -2.0253444638258027E-011_wp, -1.4017991789878334E-007_wp, & + & 3.9265259955460915E-004_wp, -6.4571737815115928E-008_wp, 7.0089204184450145E-008_wp, & + & 3.9265233232687208E-004_wp, 6.4590834777436623E-008_wp, 7.0091291955493636E-008_wp, & + &-2.0253444638258027E-011_wp, 0.61315118431143367_wp, -7.7689695353273194E-007_wp, & + & 5.4589296151605569E-011_wp, -0.30657602838911235_wp, 0.22663338413584239_wp, & + &-3.4335851513348699E-011_wp, -0.30657515591650192_wp, -0.22663260724061299_wp, & + &-1.4017991789878334E-007_wp, -7.7689695353273194E-007_wp, 0.40096663617601619_wp, & + & 3.8327586404134452E-008_wp, 0.18510543401408652_wp, -0.20048354755593945_wp, & + & 1.0185233149464886E-007_wp, -0.18510465711519453_wp, -0.20048308862513586_wp, & + & 3.9265259955460915E-004_wp, 5.4589296151605569E-011_wp, 3.8327586404134452E-008_wp, & + &-5.0343577500715762E-004_wp, 1.7015555656545986E-011_wp, -1.9169941125483937E-008_wp, & + & 1.1078317545255174E-004_wp, -7.1677131952690313E-011_wp, -1.9152730228802068E-008_wp, & + &-6.4571737815115928E-008_wp, -0.30657602838911235_wp, 0.18510543401408652_wp, & + & 1.7015555656545986E-011_wp, 0.34071042144520453_wp, -0.20586933199381116_wp, & + & 6.4554722259459369E-008_wp, -3.4134393059175372E-002_wp, 2.0763897984405841E-002_wp, & + & 7.0089204184450145E-008_wp, 0.22663338413584239_wp, -0.20048354755593945_wp, & + &-1.9169941125483937E-008_wp, -0.20586933199381116_wp, 0.18359573693614070_wp, & + &-5.0919263058966194E-008_wp, -2.0764052139551202E-002_wp, 1.6887810619957113E-002_wp, & + & 3.9265233232687208E-004_wp, -3.4335851513348699E-011_wp, 1.0185233149464886E-007_wp, & + & 1.1078317545255174E-004_wp, 6.4554722259459369E-008_wp, -5.0919263058966194E-008_wp, & + &-5.0343550777941942E-004_wp, -6.4519157645483930E-008_wp, -5.0938561726691561E-008_wp, & + & 6.4590834777436623E-008_wp, -0.30657515591650192_wp, -0.18510465711519453_wp, & + &-7.1677131952690313E-011_wp, -3.4134393059175372E-002_wp, -2.0764052139551202E-002_wp, & + &-6.4519157645483930E-008_wp, 0.34070954897294109_wp, 0.20586870925178866_wp, & + & 7.0091291955493636E-008_wp, -0.22663260724061299_wp, -0.20048308862513586_wp, & + &-1.9152730228802068E-008_wp, 2.0763897984405841E-002_wp, 1.6887810619957113E-002_wp, & + &-5.0938561726691561E-008_wp, 0.20586870925178866_wp, 0.18359527801007947_wp], & + & shape(hessian_ref)) + real(wp), parameter :: final_err_ref = 2.10070777e-6_wp + real(wp), parameter :: step = 1.0e-6_wp + + type(TMolecule) :: mol + type(TRestart) :: chk + type(TEnvironment) :: env + type(TxTBCalculator) :: calc + real(wp), allocatable :: hessian(:, :) + real(wp) :: final_err + integer :: N, i + + N = 3 * nat + call init(env) + call init(mol, sym, xyz) + + call newXTBCalculator(env, mol, calc, method=2, accuracy=1.0e-8_wp) + call newWavefunction(env, mol, calc, chk) + + allocate(hessian(N, N)) + call calc%odlrhessian(env, mol, chk, step, hessian, final_err) + + if (any(abs(hessian - hessian_ref) > thr1)) then + call test_failed(error, "Final Hessians do not match") + + print *, "--- hessian ---" + do i = 1, N + print '(*(F21.14))', hessian(i, :) + end do + + print *, "--- Ref. hessian ---" + do i = 1, N + print '(*(F21.14))', hessian_ref(i, :) + end do + end if + + if (abs(final_err - final_err_ref) > thr2) then + call test_failed(error, "Final error does not match") + print *, "--- Final error ---" + print '(*(F21.14))', final_err + print *, "--- Ref. final error ---" + print '(*(F21.14))', final_err_ref + end if +end subroutine test_o1numhess_gfn2 + +subroutine test_o1numhess_linear_h2o_gfn1(error) + type(error_type), allocatable, intent(out) :: error + integer, parameter :: nat = 3 + real(wp),parameter :: thr1 = 1.0e-9_wp, thr2 = 1.0e-5_wp + character(len=*), parameter :: sym(nat) = ["O", "H", "H"] + real(wp), parameter :: xyz(3, nat) = reshape([& + & 0.00000000000000_wp, 0.00000000000000_wp, 0.00000000000000_wp, & + & 0.00000000000000_wp, 0.00000000000000_wp, -1.81075448577205_wp, & + & 0.00000000000000_wp, 0.00000000000000_wp, 1.81075448676713_wp],& + & shape(xyz)) + real(wp), parameter :: step = 1.0e-6_wp + + type(TMolecule) :: mol + type(TRestart) :: chk + type(TEnvironment) :: env + type(TxTBCalculator) :: calc + real(wp), allocatable :: hessian(:, :), aux(:), freq(:) + real(wp) :: final_err + integer :: N, i, lwork, info + + N = 3 * nat + call init(env) + call init(mol, sym, xyz) + + call newXTBCalculator(env, mol, calc, method=1, accuracy=1.0e-8_wp) + call newWavefunction(env, mol, calc, chk) + + allocate(hessian(N, N)) + call calc%odlrhessian(env, mol, chk, step, hessian, final_err) + allocate(freq(N)) + lwork = 1 + 6*N + 2*N**2 + allocate(aux(lwork)) + call dsyev ('V', 'U', N, hessian, N, freq, aux, lwork, info) + if (count(abs(freq) < 1.0e-4_wp) /= 3) then + call test_failed(error, "Linear H2O should have exactly three ~0 freqs") + end if + + if (count(freq < -1.0e-10_wp) /= 2) then + call test_failed(error, "Linear H2O should have exactly two negative freqs") + end if + + ! freqs around -0.16 + if (freq(1) > -0.16_wp .or. freq(2) > -0.16_wp) then + call test_failed(error, "First two freqs should be negative") + print *, freq + end if +end subroutine test_o1numhess_linear_h2o_gfn1 + +subroutine test_o1numhess_linear_h2o_gfn2(error) + type(error_type), allocatable, intent(out) :: error + integer, parameter :: nat = 3 + real(wp),parameter :: thr1 = 1.0e-9_wp, thr2 = 1.0e-5_wp + character(len=*), parameter :: sym(nat) = ["O", "H", "H"] + real(wp), parameter :: xyz(3, nat) = reshape([& + & 0.00000000000000_wp, 0.00000000000000_wp, 0.00000000000000_wp, & + & 0.00000000000000_wp, 0.00000000000000_wp, -1.81075448577205_wp, & + & 0.00000000000000_wp, 0.00000000000000_wp, 1.81075448676713_wp],& + & shape(xyz)) + real(wp), parameter :: step = 1.0e-6_wp + + type(TMolecule) :: mol + type(TRestart) :: chk + type(TEnvironment) :: env + type(TxTBCalculator) :: calc + real(wp), allocatable :: hessian(:, :), aux(:), freq(:) + real(wp) :: final_err + integer :: N, i, lwork, info + + N = 3 * nat + call init(env) + call init(mol, sym, xyz) + + call newXTBCalculator(env, mol, calc, method=2, accuracy=1.0e-8_wp) + call newWavefunction(env, mol, calc, chk) + + allocate(hessian(N, N)) + call calc%odlrhessian(env, mol, chk, step, hessian, final_err) + allocate(freq(N)) + lwork = 1 + 6*N + 2*N**2 + allocate(aux(lwork)) + call dsyev ('V', 'U', N, hessian, N, freq, aux, lwork, info) + + if (count(abs(freq) < 1.0e-4_wp) /= 3) then + call test_failed(error, "Linear H2O should have exactly three ~0 freqs") + end if + + if (count(freq < -1.0e-10_wp) /= 2) then + call test_failed(error, "Linear H2O should have exactly two negative freqs") + end if + + ! freqs around -0.3 + if (freq(1) > -0.3_wp .or. freq(2) > -0.3_wp) then + call test_failed(error, "First two freqs should be negative") + end if +end subroutine test_o1numhess_linear_h2o_gfn2 + +! NOTE: the following is not used anymore because get_gradient_derivs is now private +! but might be useful for future debugging + +!!> Utility subroutine to setup neighbor list and displdir for o1numhess tests +!subroutine setup_o1numhess_test(N, displdir, ndispl_final, h0, eps, eps2) +! integer, intent(in) :: N +! real(wp), allocatable, intent(out) :: displdir(:, :) +! integer, intent(out) :: ndispl_final +! real(wp), intent(in) :: h0(:, :) +! real(wp), intent(in) :: eps, eps2 +! +! type(adj_list), allocatable :: neighborlist(:) +! real(wp), allocatable :: distmat(:, :) +! integer, allocatable :: nbcounts(:) +! integer :: i, j, max_nb, ndispl0 +! +! ! setup distmat +! allocate(distmat(N, N)) +! do i = 1, N +! do j = 1, N +! distmat(i, j) = abs(i - j) +! end do +! end do +! +! ! compute neighbor list +! call get_neighbor_list(distmat, 1.0_wp, neighborlist) +! allocate(nbcounts(N)) +! max_nb = 0 +! do i = 1, N +! nbcounts(i) = size(neighborlist(i)%neighbors) +! if (nbcounts(i) > max_nb) max_nb = nbcounts(i) +! end do +! +! ! populate displdir +! ndispl0 = 0 +! allocate(displdir(N, N)) +! call gen_displdir(N, ndispl0, h0, max_nb, neighborlist, nbcounts, eps, eps2, displdir, ndispl_final) +! +!end subroutine setup_o1numhess_test +! +!!> Utility subroutine to calculate local and final hessian for o1numhess tests +!subroutine calculate_o1numhess_hessian(mol, env, calc, chk, displdir, ndispl_final, hessian, hessian_local, step) +! type(TMolecule), intent(inout) :: mol +! type(TEnvironment), intent(inout) :: env +! type(TxTBCalculator), intent(inout) :: calc +! type(TRestart), intent(inout) :: chk +! real(wp), intent(in) :: displdir(:, :) +! integer, intent(in) :: ndispl_final +! real(wp), allocatable, intent(out) :: hessian(:, :), hessian_local(:, :) +! real(wp), intent(in) :: step +! +! real(wp), allocatable :: tmp_grad(:, :), g0(:), g(:, :), distmat(:, :) +! real(wp) :: energy, sigma(3, 3), egap +! type(scc_results) :: res +! real(wp) :: final_err +! integer :: i, j, N, ndispl0 +! +! N = 3 * mol%n +! ndispl0 = 0 +! +! ! calculate gradient derivs +! allocate(tmp_grad(3, mol%n)) +! call calc%singlepoint(env, mol, chk, -1, .false., energy, tmp_grad, sigma, egap, res) +! g0 = reshape(tmp_grad,[N]) +! allocate(g(N, ndispl_final)) +! g = 0.0_wp +! +! call calc%get_gradient_derivs(env, step, ndispl0, ndispl_final, displdir, mol, chk, g0, .false., g) +! +! ! setup distmat (needed for gen_local_hessian) +! allocate(distmat(N, N)) +! do i = 1, N +! do j = 1, N +! distmat(i, j) = abs(i - j) +! end do +! end do +! +! ! calculate local hessian +! allocate(hessian(N, N)) +! hessian = 0.0_wp +! call gen_local_hessian(env, ndispl_final, distmat, displdir, g, 1.0_wp, hessian) +! hessian_local = hessian +! call lr_loop(env, ndispl_final, g, hessian, displdir, final_err) +! +! ! print *, "final err", final_err +! +!end subroutine calculate_o1numhess_hessian +! +!subroutine test_o1numhess_gfn1(error) +! type(error_type), allocatable, intent(out) :: error +! integer, parameter :: nat = 3 +! real(wp),parameter :: thr = 1.0e-6_wp +! character(len=*), parameter :: sym(nat) = ["O", "H", "H"] +! real(wp), parameter :: xyz(3, nat) = reshape([& +! & 0.00000000000000_wp, 0.00000000034546_wp, 0.18900383618455_wp, & +! & 0.00000000000000_wp, 1.45674735348811_wp, -0.88650486059828_wp, & +! &-0.00000000000000_wp, -1.45674735383357_wp, -0.88650486086986_wp],& +! & shape(xyz)) +! ! swart model hessian from o1numhess utils +! real(wp), parameter :: h0(9, 9) = reshape([& +! & 1.1092305614e-03_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & +! &-5.5461528244e-04_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & +! &-5.5461527896e-04_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & +! & 0.0000000000e+00_wp, 4.4184751144e-01_wp, -2.7552743027e-10_wp, & +! & 0.0000000000e+00_wp, -2.2092375587e-01_wp, 1.6310770462e-01_wp, & +! & 0.0000000000e+00_wp, -2.2092375557e-01_wp, -1.6310770435e-01_wp, & +! & 0.0000000000e+00_wp, -2.7552743027e-10_wp, 2.9417034746e-01_wp, & +! & 0.0000000000e+00_wp, 1.4319582461e-01_wp, -1.4708517387e-01_wp, & +! & 0.0000000000e+00_wp, -1.4319582434e-01_wp, -1.4708517359e-01_wp, & +! &-5.5461528244e-04_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & +! & 1.6724709350e-03_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & +! &-1.1178556526e-03_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & +! & 0.0000000000e+00_wp, -2.2092375587e-01_wp, 1.4319582461e-01_wp, & +! & 0.0000000000e+00_wp, 2.3323207511e-01_wp, -1.5315176462e-01_wp, & +! & 0.0000000000e+00_wp, -1.2308319237e-02_wp, 9.9559400089e-03_wp, & +! & 0.0000000000e+00_wp, 1.6310770462e-01_wp, -1.4708517387e-01_wp, & +! & 0.0000000000e+00_wp, -1.5315176462e-01_wp, 1.3375368579e-01_wp, & +! & 0.0000000000e+00_wp, -9.9559400048e-03_wp, 1.3331488088e-02_wp, & +! &-5.5461527896e-04_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & +! &-1.1178556526e-03_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & +! & 1.6724709315e-03_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & +! & 0.0000000000e+00_wp, -2.2092375557e-01_wp, -1.4319582434e-01_wp, & +! & 0.0000000000e+00_wp, -1.2308319237e-02_wp, -9.9559400048e-03_wp, & +! & 0.0000000000e+00_wp, 2.3323207480e-01_wp, 1.5315176434e-01_wp, & +! & 0.0000000000e+00_wp, -1.6310770435e-01_wp, -1.4708517359e-01_wp, & +! & 0.0000000000e+00_wp, 9.9559400089e-03_wp, 1.3331488088e-02_wp, & +! & 0.0000000000e+00_wp, 1.5315176434e-01_wp, 1.3375368550e-01_wp],& +! & shape(h0)) +! real(wp), parameter :: hessian_local_ref(9, 9) = reshape([& +! & 3.51981175325187e-04_wp, -3.76511734388845e-03_wp, 3.81178115691305e-04_wp,& +! & -2.37598469686780e-04_wp, 2.52570715380943e-03_wp, -3.32541413989657e-04_wp,& +! & 0.00000000000000e+00_wp, 0.00000000000000e+00_wp, 0.00000000000000e+00_wp,& +! & -3.76511734388845e-03_wp, -6.72401397966386e-02_wp, -2.11729004550184e-01_wp,& +! & 1.32115390027701e-02_wp, 8.06252321926636e-03_wp, 7.39146674965733e-03_wp,& +! & 1.17788921786219e-04_wp, 0.00000000000000e+00_wp, 0.00000000000000e+00_wp,& +! & 3.81178115691305e-04_wp, -2.11729004550184e-01_wp, 4.63279981243663e-01_wp,& +! & 2.00861682675189e-02_wp, 1.75152612759093e-01_wp, -5.17419081415414e-03_wp,& +! & 9.72230292022307e-04_wp, 8.49401740708410e-04_wp, 0.00000000000000e+00_wp,& +! & -2.37598469686780e-04_wp, 1.32115390027701e-02_wp, 2.00861682675189e-02_wp,& +! & 2.49132380283098e-03_wp, -1.15993237268750e-02_wp, 2.38421110728877e-02_wp,& +! & -1.70620005390799e-14_wp, 5.64969948975101e-04_wp, -1.06083536905192e-04_wp,& +! & 2.52570715380943e-03_wp, 8.06252321926636e-03_wp, 1.75152612759093e-01_wp,& +! & -1.15993237268750e-02_wp, -5.36618040845405e-02_wp, -1.22992832629143e-01_wp,& +! & -1.28817650172161e-02_wp, -1.41730858229258e-04_wp, 4.94454130056628e-03_wp,& +! & -3.32541413989657e-04_wp, 7.39146674965733e-03_wp, -5.17419081415414e-03_wp,& +! & 2.38421110728877e-02_wp, -1.22992832629143e-01_wp, 2.84196776383033e-01_wp,& +! & 1.79323845243361e-02_wp, 1.49966320866984e-01_wp, 3.13392912791258e-03_wp,& +! & 0.00000000000000e+00_wp, 1.17788921786219e-04_wp, 9.72230292022307e-04_wp,& +! & -1.70620005390799e-14_wp, -1.28817650172161e-02_wp, 1.79323845243361e-02_wp,& +! & 4.76557582555649e-05_wp, 8.95077909660287e-03_wp, 1.54823774005412e-02_wp,& +! & 0.00000000000000e+00_wp, 0.00000000000000e+00_wp, 8.49401740708410e-04_wp,& +! & 5.64969948975101e-04_wp, -1.41730858229258e-04_wp, 1.49966320866984e-01_wp,& +! & 8.95077909660287e-03_wp, 7.32108733232320e-02_wp, 8.32366313319442e-02_wp,& +! & 0.00000000000000e+00_wp, 0.00000000000000e+00_wp, 0.00000000000000e+00_wp,& +! & -1.06083536905192e-04_wp, 4.94454130056628e-03_wp, 3.13392912791258e-03_wp,& +! & 1.54823774005412e-02_wp, 8.32366313319442e-02_wp, -9.34713030397501e-02_wp],& +! & shape(hessian_local_ref)) +! real(wp), parameter :: hessian_ref(9, 9) = reshape([& +! & 3.58438579043206e-04_wp, -3.81039356197628e-03_wp, 4.03399313822165e-04_wp,& +! & -2.82476978351356e-04_wp, 3.84811786546152e-03_wp, -7.63006730622276e-04_wp,& +! & 2.31299048839153e-04_wp, 4.84032295451731e-04_wp, 1.32189016912669e-04_wp,& +! & -3.81039356197628e-03_wp, -6.72927252587342e-02_wp, -2.11638325546983e-01_wp,& +! & 1.33755408386769e-02_wp, 9.29003639664687e-03_wp, 1.13194001517243e-02_wp,& +! & 1.68329797547482e-04_wp, 3.50224644185952e-04_wp, -1.00445342525072e-03_wp,& +! & 4.03399313822165e-04_wp, -2.11638325546983e-01_wp, 4.63339799742256e-01_wp,& +! & 2.00825620440430e-02_wp, 1.78712614527116e-01_wp, -6.07451375400960e-03_wp,& +! & 1.49362842611287e-03_wp, 2.00250342612253e-03_wp, 5.14406818716446e-04_wp,& +! & -2.82476978351356e-04_wp, 1.33755408386769e-02_wp, 2.00825620440430e-02_wp,& +! & 2.47276791227794e-03_wp, -1.16796282245497e-02_wp, 2.43427547421269e-02_wp,& +! & -1.85558905700834e-05_wp, 7.76482115758251e-04_wp, -2.82293395959265e-04_wp,& +! & 3.84811786546152e-03_wp, 9.29003639664687e-03_wp, 1.78712614527116e-01_wp,& +! & -1.16796282245497e-02_wp, -5.37238742371844e-02_wp, -1.23025151971481e-01_wp,& +! & -1.32197048151783e-02_wp, -2.37180362396234e-04_wp, 7.63607499039816e-03_wp,& +! & -7.63006730622276e-04_wp, 1.13194001517243e-02_wp, -6.07451375400960e-03_wp,& +! & 2.43427547421269e-02_wp, -1.23025151971481e-01_wp, 2.84273693850240e-01_wp,& +! & 1.79561859722289e-02_wp, 1.52928583030049e-01_wp, 3.54908290642412e-03_wp,& +! & 2.31299048839153e-04_wp, 1.68329797547482e-04_wp, 1.49362842611287e-03_wp,& +! & -1.85558905700834e-05_wp, -1.32197048151783e-02_wp, 1.79561859722289e-02_wp,& +! & 2.90998677025632e-05_wp, 8.85720749101923e-03_wp, 1.57516020166363e-02_wp,& +! & 4.84032295451731e-04_wp, 3.50224644185952e-04_wp, 2.00250342612253e-03_wp,& +! & 7.76482115758251e-04_wp, -2.37180362396234e-04_wp, 1.52928583030049e-01_wp,& +! & 8.85720749101923e-03_wp, 7.31255602924301e-02_wp, 8.32609561079180e-02_wp,& +! & 1.32189016912669e-04_wp, -1.00445342525072e-03_wp, 5.14406818716446e-04_wp,& +! & -2.82293395959265e-04_wp, 7.63607499039816e-03_wp, 3.54908290642412e-03_wp,& +! & 1.57516020166363e-02_wp, 8.32609561079180e-02_wp, -9.33774159826147e-02_wp],& +! & shape(hessian_ref)) +! real(wp), parameter :: eps = 1.0e-8_wp, eps2 = 1.0e-15_wp, step = 1.0e-6_wp +! +! type(TMolecule) :: mol +! type(TRestart) :: chk +! type(TEnvironment) :: env +! type(TxTBCalculator) :: calc +! real(wp), allocatable :: displdir(:, :), hessian(:, :), hessian_local(:, :) +! integer :: i, N, ndispl_final +! +! call init(env) +! call init(mol, sym, xyz) +! +! call setup_o1numhess_test(3*mol%n, displdir, ndispl_final, h0, eps, eps2) +! +! ! use GFN1 +! call newXTBCalculator(env, mol, calc, method=1, accuracy=1.0e-8_wp) +! call newWavefunction(env, mol, calc, chk) +! +! call calculate_o1numhess_hessian(mol, env, calc, chk, displdir, ndispl_final, hessian, hessian_local, step) +! +! ! compare +! N = 3 * nat +! if (any(abs(hessian_local - hessian_local_ref) > thr)) then +! call test_failed(error, "Local Hessians do not match") +! +! print *, "--- hessian ---" +! do i = 1, N +! print '(*(F21.14))', hessian_local(i, :) +! end do +! +! print *, "--- Ref. hessian ---" +! do i = 1, N +! print '(*(F21.14))', hessian_local_ref(i, :) +! end do +! end if +! +! if (any(abs(hessian - hessian_ref) > thr)) then +! call test_failed(error, "Final Hessians do not match") +! +! print *, "--- hessian ---" +! do i = 1, N +! print '(*(F21.14))', hessian(i, :) +! end do +! +! print *, "--- Ref. hessian ---" +! do i = 1, N +! print '(*(F21.14))', hessian_ref(i, :) +! end do +! end if +!end subroutine test_o1numhess_gfn1 +! +!subroutine test_o1numhess_gfn2(error) +! type(error_type), allocatable, intent(out) :: error +! integer, parameter :: nat = 3 +! real(wp),parameter :: thr = 1.0e-6_wp +! character(len=*), parameter :: sym(nat) = ["O", "H", "H"] +! real(wp), parameter :: xyz(3, nat) = reshape([& +! & 0.00000000000000_wp, 0.00000000034546_wp, 0.18900383618455_wp, & +! & 0.00000000000000_wp, 1.45674735348811_wp, -0.88650486059828_wp, & +! &-0.00000000000000_wp, -1.45674735383357_wp, -0.88650486086986_wp],& +! & shape(xyz)) +! ! swart model hessian from o1numhess utils +! real(wp), parameter :: h0(9, 9) = reshape([& +! & 1.1092305614e-03_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & +! &-5.5461528244e-04_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & +! &-5.5461527896e-04_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & +! & 0.0000000000e+00_wp, 4.4184751144e-01_wp, -2.7552743027e-10_wp, & +! & 0.0000000000e+00_wp, -2.2092375587e-01_wp, 1.6310770462e-01_wp, & +! & 0.0000000000e+00_wp, -2.2092375557e-01_wp, -1.6310770435e-01_wp, & +! & 0.0000000000e+00_wp, -2.7552743027e-10_wp, 2.9417034746e-01_wp, & +! & 0.0000000000e+00_wp, 1.4319582461e-01_wp, -1.4708517387e-01_wp, & +! & 0.0000000000e+00_wp, -1.4319582434e-01_wp, -1.4708517359e-01_wp, & +! &-5.5461528244e-04_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & +! & 1.6724709350e-03_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & +! &-1.1178556526e-03_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & +! & 0.0000000000e+00_wp, -2.2092375587e-01_wp, 1.4319582461e-01_wp, & +! & 0.0000000000e+00_wp, 2.3323207511e-01_wp, -1.5315176462e-01_wp, & +! & 0.0000000000e+00_wp, -1.2308319237e-02_wp, 9.9559400089e-03_wp, & +! & 0.0000000000e+00_wp, 1.6310770462e-01_wp, -1.4708517387e-01_wp, & +! & 0.0000000000e+00_wp, -1.5315176462e-01_wp, 1.3375368579e-01_wp, & +! & 0.0000000000e+00_wp, -9.9559400048e-03_wp, 1.3331488088e-02_wp, & +! &-5.5461527896e-04_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & +! &-1.1178556526e-03_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & +! & 1.6724709315e-03_wp, 0.0000000000e+00_wp, 0.0000000000e+00_wp, & +! & 0.0000000000e+00_wp, -2.2092375557e-01_wp, -1.4319582434e-01_wp, & +! & 0.0000000000e+00_wp, -1.2308319237e-02_wp, -9.9559400048e-03_wp, & +! & 0.0000000000e+00_wp, 2.3323207480e-01_wp, 1.5315176434e-01_wp, & +! & 0.0000000000e+00_wp, -1.6310770435e-01_wp, -1.4708517359e-01_wp, & +! & 0.0000000000e+00_wp, 9.9559400089e-03_wp, 1.3331488088e-02_wp, & +! & 0.0000000000e+00_wp, 1.5315176434e-01_wp, 1.3375368550e-01_wp],& +! & shape(h0)) +! real(wp), parameter :: hessian_local_ref(9, 9) = reshape([& +! & 3.19677112844234e-04_wp, -3.32342131309818e-03_wp, -2.67790616248500e-05_wp,& +! & -1.93324060431286e-04_wp, 2.34887629241175e-03_wp, -2.97382602124213e-04_wp,& +! & 0.00000000000000e+00_wp, 0.00000000000000e+00_wp, 0.00000000000000e+00_wp,& +! & -3.32342131309818e-03_wp, -6.30870143425176e-02_wp, -1.99496626493542e-01_wp,& +! & 1.20902490299375e-02_wp, 7.47363090613361e-03_wp, 6.85160128840844e-03_wp,& +! & 8.90280217865149e-05_wp, 0.00000000000000e+00_wp, 0.00000000000000e+00_wp,& +! & -2.67790616248500e-05_wp, -1.99496626493542e-01_wp, 4.63216871841495e-01_wp,& +! & 1.92444959775377e-02_wp, 1.62320366204895e-01_wp, -4.80311579353320e-03_wp,& +! & 9.25923730998759e-04_wp, 6.23997695176231e-04_wp, 0.00000000000000e+00_wp,& +! & -1.93324060431286e-04_wp, 1.20902490299375e-02_wp, 1.92444959775377e-02_wp,& +! & 2.33820095994906e-03_wp, -1.06506356763412e-02_wp, 2.25289791347748e-02_wp,& +! & -1.55391471185750e-14_wp, 5.73518635910525e-04_wp, -6.78104372076033e-05_wp,& +! & 2.34887629241175e-03_wp, 7.47363090613361e-03_wp, 1.62320366204895e-01_wp,& +! & -1.06506356763412e-02_wp, -5.41413149509843e-02_wp, -1.20812305434173e-01_wp,& +! & -1.30893376495030e-02_wp, -1.41183939391319e-04_wp, 4.92546103224633e-03_wp,& +! & -2.97382602124213e-04_wp, 6.85160128840844e-03_wp, -4.80311579353320e-03_wp,& +! & 2.25289791347748e-02_wp, -1.20812305434173e-01_wp, 2.79913227822072e-01_wp,& +! & 1.87438497579491e-02_wp, 1.49387622567730e-01_wp, 3.12183574957329e-03_wp,& +! & 0.00000000000000e+00_wp, 8.90280217865149e-05_wp, 9.25923730998759e-04_wp,& +! & -1.55391471185750e-14_wp, -1.30893376495030e-02_wp, 1.87438497579491e-02_wp,& +! & -4.79319030380975e-06_wp, 8.88421644367883e-03_wp, 1.65261717538513e-02_wp,& +! & 0.00000000000000e+00_wp, 0.00000000000000e+00_wp, 6.23997695176231e-04_wp,& +! & 5.73518635910525e-04_wp, -1.41183939391319e-04_wp, 1.49387622567730e-01_wp,& +! & 8.88421644367883e-03_wp, 7.07044219384617e-02_wp, 8.37522763859865e-02_wp,& +! & 0.00000000000000e+00_wp, 0.00000000000000e+00_wp, 0.00000000000000e+00_wp,& +! & -6.78104372076033e-05_wp, 4.92546103224633e-03_wp, 3.12183574957329e-03_wp,& +! & 1.65261717538513e-02_wp, 8.37522763859865e-02_wp, -1.01307468842741e-01_wp],& +! & shape(hessian_local_ref)) +! real(wp), parameter :: hessian_ref(9, 9) = reshape([& +! & 3.21202548348861e-04_wp, -3.36143522890183e-03_wp, -1.61434670765408e-05_wp,& +! & -2.33476898312511e-04_wp, 3.58311191231894e-03_wp, -6.80597145923440e-04_wp,& +! & 2.25424943548716e-04_wp, 3.90896402245910e-04_wp, 8.85821968433675e-05_wp,& +! & -3.36143522890183e-03_wp, -6.31369977795672e-02_wp, -1.99406199899265e-01_wp,& +! & 1.22397867307581e-02_wp, 8.60841380834760e-03_wp, 1.04867482257833e-02_wp,& +! & 1.10716609923727e-04_wp, 2.44005464184140e-04_wp, -7.27804274818003e-04_wp,& +! & -1.61434670765408e-05_wp, -1.99406199899265e-01_wp, 4.63276927090022e-01_wp,& +! & 1.92372026481329e-02_wp, 1.65623784950145e-01_wp, -5.64376804607281e-03_wp,& +! & 1.41862921621685e-03_wp, 1.48865713775440e-03_wp, 4.03179144287053e-04_wp,& +! & -2.33476898312511e-04_wp, 1.22397867307581e-02_wp, 1.92372026481329e-02_wp,& +! & 2.32016668873703e-03_wp, -1.07232346626970e-02_wp, 2.30053559824699e-02_wp,& +! & -1.80342712296196e-05_wp, 7.98663420130482e-04_wp, -1.95601212615882e-04_wp,& +! & 3.58311191231894e-03_wp, 8.60841380834760e-03_wp, 1.65623784950145e-01_wp,& +! & -1.07232346626970e-02_wp, -5.42028871409179e-02_wp, -1.20845949315161e-01_wp,& +! & -1.34237233887938e-02_wp, -2.35976097335490e-04_wp, 7.60816561498387e-03_wp,& +! & -6.80597145923440e-04_wp, 1.04867482257833e-02_wp, -5.64376804607281e-03_wp,& +! & 2.30053559824699e-02_wp, -1.20845949315161e-01_wp, 2.79989829800501e-01_wp,& +! & 1.87696470230527e-02_wp, 1.52336761147164e-01_wp, 3.53512397590933e-03_wp,& +! & 2.25424943548716e-04_wp, 1.10716609923727e-04_wp, 1.41862921621685e-03_wp,& +! & -1.80342712296196e-05_wp, -1.34237233887938e-02_wp, 1.87696470230527e-02_wp,& +! & -2.28274615199358e-05_wp, 8.79966116458134e-03_wp, 1.68157017730541e-02_wp,& +! & 3.90896402245910e-04_wp, 2.44005464184140e-04_wp, 1.48865713775440e-03_wp,& +! & 7.98663420130482e-04_wp, -2.35976097335490e-04_wp, 1.52336761147164e-01_wp,& +! & 8.79966116458134e-03_wp, 7.06197606988344e-02_wp, 8.37783234293568e-02_wp,& +! & 8.85821968433675e-05_wp, -7.27804274818003e-04_wp, 4.03179144287053e-04_wp,& +! & -1.95601212615882e-04_wp, 7.60816561498387e-03_wp, 3.53512397590933e-03_wp,& +! & 1.68157017730541e-02_wp, 8.37783234293568e-02_wp, -1.01213366096153e-01_wp],& +! & shape(hessian_ref)) +! real(wp), parameter :: eps = 1.0e-8_wp, eps2 = 1.0e-15_wp, step = 1.0e-6_wp +! +! type(TMolecule) :: mol +! type(TRestart) :: chk +! type(TEnvironment) :: env +! type(TxTBCalculator) :: calc +! real(wp), allocatable :: displdir(:, :), hessian(:, :), hessian_local(:, :) +! real(wp) :: final_err +! integer :: i, N, ndispl_final +! +! N = 3 * nat +! call init(env) +! call init(mol, sym, xyz) +! +! call setup_o1numhess_test(3*mol%n, displdir, ndispl_final, h0, eps, eps2) +! +! ! use GFN2 +! call newXTBCalculator(env, mol, calc, method=2, accuracy=1.0e-8_wp) +! call newWavefunction(env, mol, calc, chk) +! +! call calculate_o1numhess_hessian(mol, env, calc, chk, displdir, ndispl_final, hessian, hessian_local, step) +! +! ! compare +! if (any(abs(hessian_local - hessian_local_ref) > thr)) then +! call test_failed(error, "Local Hessians do not match") +! +! print *, "--- hessian ---" +! do i = 1, N +! print '(*(F21.14))', hessian_local(i, :) +! end do +! +! print *, "--- Ref. hessian ---" +! do i = 1, N +! print '(*(F21.14))', hessian_local_ref(i, :) +! end do +! end if +! +! if (any(abs(hessian - hessian_ref) > thr)) then +! call test_failed(error, "Final Hessians do not match") +! +! print *, "--- hessian ---" +! do i = 1, N +! print '(*(F21.14))', hessian(i, :) +! end do +! +! print *, "--- Ref. hessian ---" +! do i = 1, N +! print '(*(F21.14))', hessian_ref(i, :) +! end do +! end if +!end subroutine test_o1numhess_gfn2 + end module test_hessian