Merge branch 'project_out_SC_merge' into 'development' (b05e753c) · Commits · eT / eT

changelog.md

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		@@ -258,6 +258,7 @@ some roots were converged and others below the linear dependence threshold. eT-p
		- Optimized ``get_eri_1der_libcint`` to remove redundancy in derivative integrals. eT-program/eT!1511
		- Optimized low memory CC2 Jacobian by replacing c1 transformations of the integrals, by c1 transformations of the Cholesky vectors. eT-program/eT!1518, eT-program/eT!1519, eT-program/eT!1520
		- Optimized cube file generator. eT-program/eT!1543
		- SC-QED-HF convergence is more robust by projecting out eta redundancies. eT-program/eT!!1557

		### Documentation
		- Updates to README. eT-program/eT!1247, eT-program/eT!1487

cmake/TestseT.cmake

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		@@ -184,6 +184,8 @@ add_eT_runtest(restart_qed_ccsd_es_energy "eT;short;qed;ccsd;g
		add_eT_runtest(sc_qed_hf_energy "eT;short;sc-qed;hf")
		add_eT_runtest(restart_sc_qed_hf "eT;short;restart;sc-qed;hf")
		#
		add_eT_runtest(sc_qed_hf_intensivity_symmetry "eT;short;sc-qed;hf")
		#
		add_eT_runtest(mp2_energy "eT;short;hf;mp2")
		add_eT_runtest(mp2_energy_qmmmnopol "eT;short;hf;mp2;qmmm;mmnopol")
		add_eT_runtest(mp2_energy_qmfq "eT;short;hf;mp2;qmmm;fq")

src/wavefunctions/sc_qed_hf/sc_qed_hf_class.F90

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		@@ -1145,25 +1145,45 @@ contains
		!!
		!! Constructs the eta-eta Hessian matrix (E^(2)):
		!! E^(2)_rs = 1/omega^2 <R\|[E_ss(b-b^+),[E_rr(b-b^+),H_SC]]\|R>.
		!! Multiply the invert of it ((E^(2))^-1) to minus the gradient.
		!! The result is the second order step for the eta parameters.
		!!
		!! eta_step = - ((E^(2))^-1)*eta_grad
		!! The eigenvalue problem is projected in the space orthogonal
		!! to the one spanned by the eta redundancies:
		!! E^(2) * eta_step = - eta_grad -->
		!! --> PE^(2) Peta_step = - Peta_grad.
		!!
		!! The projector P is obtaiened after the diagonalization of
		!! overlap matrix S_pq = <R\|E_pp E_qq\|R>.
		!!
		!! The projected Hessian P*E^(2) is level-shifed so to ensure
		!! invertibility in case of singular values due to redundancies.
		!!
		!! The projected step P*eta_step is obtained solving:
		!! Peta_step = - (PE^(2) + level_shiftI)^-1 P*eta_grad.
		!!
		use array_utilities, only: invert
		use array_initialization, only: identity_array
		use parameters

		implicit none

		class(sc_qed_hf) :: wf

		real(dp), dimension(:,:), allocatable :: hessian, D, h, hessian_inverse
		real(dp), dimension(:,:), allocatable :: D, h, work, overlap, P, identity

		real(dp), dimension(:,:), allocatable :: hessian, projected_hessian, hessian_inverse

		real(dp), dimension(wf%n_mo), intent(out) :: step

		real(dp) :: gaussian_factor, common_addend
		real(dp), dimension(:), allocatable :: eigenvalues, projected_gradient

		real(dp) :: gaussian_factor, common_addend, ddot

		integer :: r, s, q, t
		real(dp), parameter :: threshold = 1.0d-7
		real(dp), parameter :: level_shift = 1.0d-6

		logical :: regularize_Hessian = .False.

		integer :: r, s, q, t, info

		call mem%alloc(D, wf%n_mo, wf%n_mo)
		call wf%construct_density_dipole_basis(D)
		@@ -1174,6 +1194,8 @@ contains

		call mem%alloc(hessian, wf%n_mo, wf%n_mo)

		! Calculation of the Hessian.

		!$omp parallel do private(r, s, q, t, gaussian_factor, common_addend)
		do r = 1, wf%n_mo

		@@ -1218,12 +1240,126 @@ contains
		!$omp end parallel do

		call mem%dealloc(h)

		call mem%alloc(overlap, wf%n_mo, wf%n_mo, set_zero=.True.)

		! Overlap matrix S_pq = <R\|E_pp E_qq\|R> = d_ppqq + D_pq delta_pq.

		!$omp parallel do private(q)
		do q = 1, wf%n_mo
		overlap(q,q) = D(q,q)
		enddo
		!$omp end parallel do

		!$omp parallel do private(q, r)
		do q = 1, wf%n_mo
		do r = 1, wf%n_mo
		overlap(q,r) = overlap(q,r) + (D(q,q)D(r,r)-halfD(q,r)*D(r,q))
		enddo
		enddo
		!$omp end parallel do

		call mem%dealloc(D)

		call mem%alloc(work, wf%n_mo, wf%n_mo)
		call mem%alloc(eigenvalues, wf%n_mo)

		call dsyev('V', 'U', &
		wf%n_mo, &
		overlap, &
		wf%n_mo, &
		eigenvalues, &
		work, &
		wf%n_mo**2, &
		info)

		call mem%dealloc(work)

		call mem%alloc(P, wf%n_mo, wf%n_mo)

		! Projector P = I - sum_i vT_i*v_i where vi are eigenvector
		! associated to zero eigenvalues of the overlap matrix S.

		call identity_array(P, wf%n_mo)

		do q = 1, wf%n_mo

		if (abs(eigenvalues(q)) < threshold) then
		regularize_Hessian = .True.

		call dger(wf%n_mo, &
		wf%n_mo, &
		-one, &
		overlap(:,q), &
		1, &
		overlap(:,q), &
		1, &
		P, &
		wf%n_mo)
		end if

		end do

		call mem%dealloc(eigenvalues)
		call mem%dealloc(overlap)

		call mem%alloc(projected_gradient, wf%n_mo)
		call mem%alloc(projected_hessian, wf%n_mo, wf%n_mo)

		! Projecting the gradient eta_grad --> P*eta_grad.

		call dgemm('N','N', &
		wf%n_mo, &
		1, &
		wf%n_mo, &
		one, &
		P, &
		wf%n_mo, &
		wf%eta_gradient, &
		wf%n_mo, &
		zero, &
		projected_gradient, &
		wf%n_mo)

		! Projecting the Hessian E^(2) --> P*E^(2).

		call dgemm('N','N', &
		wf%n_mo, &
		wf%n_mo, &
		wf%n_mo, &
		one, &
		P, &
		wf%n_mo, &
		hessian, &
		wf%n_mo, &
		zero, &
		projected_hessian, &
		wf%n_mo)

		call dcopy(wf%n_mo, projected_gradient, 1, wf%eta_gradient, 1)
		call dcopy(wf%n_mo**2, projected_hessian, 1, hessian, 1)

		call mem%dealloc(projected_gradient)
		call mem%dealloc(projected_hessian)
		call mem%dealloc(P)

		! If Hessian is singular, level-shift is done.

		if (regularize_Hessian) then
		call mem%alloc(identity, wf%n_mo, wf%n_mo)
		call identity_array(identity, wf%n_mo)

		hessian = hessian + identity * level_shift

		call mem%dealloc(identity)
		endif

		call mem%alloc(hessian_inverse, wf%n_mo, wf%n_mo)

		call invert(hessian_inverse, hessian, wf%n_mo)

		! Calculating the projected step P*eta_step.

		call dgemm('N','N', &
		wf%n_mo, &
		1, &

tests/sc_qed_hf_intensivity_symmetry/result/sc_qed_hf_intensivity_symmetry.mo_information.out

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File added.

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tests/sc_qed_hf_intensivity_symmetry/result/sc_qed_hf_intensivity_symmetry.out

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		eT 2.0 - an electronic structure program

		------------------------------------------------------------------------
		Author list in alphabetical order:
		------------------------------------------------------------------------
		J. H. Andersen, S. Angelico, A. Balbi, A. Barlini, A. Bianchi, C.
		Cappelli, M. Castagnola, S. Coriani, S. D. Folkestad, Y. El Moutaoukal,
		T. Giovannini, L. Goletto, T. S. Haugland, A. Hutcheson, I-M. Høyvik,
		E. F. Kjønstad, H. Koch, M. T. Lexander, G. Marrazzini, T. Moitra,
		R. H. Myhre, Y. Os, A. C. Paul, R. Paul, J. Pedersen, M. Rinaldi,
		R. R. Riso, S. Roet, E. Ronca, F. Rossi, B. S. Sannes, M. Scavino,
		A. K. Schnack-Petersen, A. S. Skeidsvoll, J. H. M. Trabski, Å. H.
		Tveten
		------------------------------------------------------------------------
		J. Chem. Phys. 152, 184103 (2020); https://doi.org/10.1063/5.0004713


		This is eT 2.0.0 A (development)
		-------------------------------------------------------------
		Configuration date: 2025-04-14 11:11:32 UTC +02:00
		Git branch: project_out_SC_merge
		Git hash: 9742e869970d1b82624a1bb5de4dc3bb3f38aa6d
		Fortran compiler: GNU 11.4.0
		C compiler: GNU 11.4.0
		C++ compiler: GNU 11.4.0
		LAPACK type: SYSTEM_NATIVE
		BLAS type: SYSTEM_NATIVE
		OEI type: libcint
		ERI type: libcint
		64-bit integers: OFF
		OpenMP: ON
		PCM: OFF
		Forced batching: OFF
		Runtime checks: OFF
		Initializing to NAN: OFF
		-------------------------------------------------------------

		Calculation start:2025-04-14 11:27:52 UTC +02:00

		Running on 12 OMP threads


		:: Input file
		=============

		Note: geometry section is excluded from this print.

		- system
		charge: 0

		- do
		ground state

		- memory
		available: 8

		- solver cholesky
		threshold: 1.0d-12

		- solver scf
		algorithm: scf-diis
		energy threshold: 1.0d-10
		residual threshold: 1.0d-10
		max iterations: 1000
		write orbitals

		- method
		sc-qed-hf

		- boson
		modes: 1
		frequency: {0.5}
		polarization: {0.270, -0.892, 0.363}
		coupling: {0.1}

		Memory available for calculation: 8.000000 GB


		:: SC-QED-RHF wavefunction
		==========================

		================================================================================
		Geometry (angstrom)
		================================================================================
		Atom X Y Z #internal #input
		================================================================================
		Basis: sto-3g
		O 1.151306358200 0.596196864600 -0.528619881900 1 1
		C 2.335856168400 -0.050626472200 -0.155984189800 2 2
		C 0.000000000000 0.000000000000 0.000000000000 3 3
		H 2.483504302300 -0.053830165400 0.945131400800 4 4
		H 3.176554004200 0.488613979100 -0.617545858200 5 5
		H 2.364079626500 -1.106062129300 -0.501707806000 6 6
		H 0.000000000000 0.000000000000 1.110975264200 7 7
		H -0.119418084700 -1.052237046200 -0.335861183600 8 8
		H -0.870532905900 0.576327038500 -0.347292217100 9 9
		O 1001.151306358200 0.596196864600 -0.528619881900 10 10
		C 1002.335856168400 -0.050626472200 -0.155984189800 11 11
		C 1000.000000000000 0.000000000000 0.000000000000 12 12
		H 1002.483504302300 -0.053830165400 0.945131400800 13 13
		H 1003.176554004200 0.488613979100 -0.617545858200 14 14
		H 1002.364079626500 -1.106062129300 -0.501707806000 15 15
		H 1000.000000000000 0.000000000000 1.110975264200 16 16
		H 999.880581915300 -1.052237046200 -0.335861183600 17 17
		H 999.129467094100 0.576327038500 -0.347292217100 18 18
		================================================================================

		================================================================================
		Geometry (a.u.)
		================================================================================
		Atom X Y Z #internal #input
		================================================================================
		Basis: sto-3g
		O 2.175653702468 1.126648790418 -0.998946800791 1 1
		C 4.414128424652 -0.095670167111 -0.294767398484 2 2
		C 0.000000000000 0.000000000000 0.000000000000 3 3
		H 4.693142960526 -0.101724269846 1.786039499239 4 4
		H 6.002817087828 0.923346601133 -1.166992541357 5 5
		H 4.467463030749 -2.090154501130 -0.948090347896 6 6
		H 0.000000000000 0.000000000000 2.099438980504 7 7
		H -0.225667474403 -1.988439835439 -0.634685652876 8 8
		H -1.645068774573 1.089100260947 -0.656287175512 9 9
		O 1891.901778267530 1.126648790418 -0.998946800791 10 10
		C 1894.140252989714 -0.095670167111 -0.294767398484 11 11
		C 1889.726124565062 0.000000000000 0.000000000000 12 12
		H 1894.419267525588 -0.101724269846 1.786039499239 13 13
		H 1895.728941652890 0.923346601133 -1.166992541357 14 14
		H 1894.193587595811 -2.090154501130 -0.948090347896 15 15
		H 1889.726124565062 0.000000000000 2.099438980504 16 16
		H 1889.500457090659 -1.988439835439 -0.634685652876 17 17
		H 1888.081055790489 1.089100260947 -0.656287175512 18 18
		================================================================================

		- Cholesky decomposition of AO overlap to get linearly independent AOs:

		Linear dependence threshold: 0.10E-05
		Number of atomic orbitals: 42
		Number of orthonormal atomic orbitals: 42

		- Molecular orbital details:

		Number of occupied orbitals: 26
		Number of virtual orbitals: 16
		Number of molecular orbitals: 42


		Generating initial SAD density
		==============================


		Determining reference state
		===========================

		- Setting initial AO density to sad

		Energy of initial guess: -302.647732621831
		Number of electrons in guess: 52.000000000000

		- Screening and integral thresholds:

		Coulomb screening threshold: 0.1000E-15
		Exchange screening threshold: 0.1000E-13
		Cumulative Fock threshold: 0.0000E+00
		ERI precision: 0.1000E-15
		One-electron integral precision: 0.1000E-20

		Self-consistent field solver
		----------------------------

		A Self-consistent field solver that solves an eigenvalue equations:
		F(C) C = C e.

		- SCF solver settings:

		Maximum iterations: 1000
		Acceleration type: diis

		- Convergence thresholds:
		Residual threshold: 0.1000E-09
		Energy threshold: 0.1000E-09

		- DIIS tool settings:

		DIIS dimension: 8
		Storage (solver scf_errors): memory
		Storage (solver scf_parameters): memory

		Iteration Energy (a.u.) Max(grad.) Delta E (a.u.)
		---------------------------------------------------------------
		1 -304.058899719938 0.2273E+00 0.3041E+03
		2 -304.214475785147 0.1726E+00 0.1556E+00
		3 -304.221639876684 0.3194E-01 0.7164E-02
		4 -304.222964060590 0.3542E-02 0.1324E-02
		5 -304.223123421708 0.4696E-02 0.1594E-03
		6 -304.223137388731 0.2865E-03 0.1397E-04
		7 -304.223137571511 0.1805E-04 0.1828E-06
		8 -304.223137577751 0.1779E-04 0.6241E-08
		9 -304.223137578153 0.1038E-05 0.4020E-09
		10 -304.223137578175 0.6553E-06 0.2115E-10
		11 -304.223137578175 0.4674E-07 0.7390E-12
		12 -304.223137578175 0.5930E-08 0.2274E-12
		13 -304.223137578176 0.1895E-08 0.5684E-12
		14 -304.223137578174 0.5708E-09 0.1137E-11
		15 -304.223137578176 0.2121E-09 0.1137E-11
		16 -304.223137578175 0.1010E-10 0.7390E-12
		---------------------------------------------------------------
		Convergence criterion met in 16 iterations!

		- Summary of SC-QED-RHF wavefunction energetics (a.u.):

		HOMO-LUMO gap: 0.909366882695
		Nuclear repulsion energy: 168.084142730147
		Electronic energy: -472.307280308322
		Total energy: -304.223137578175

		- Photon parameters and properties

		Optimize photons displacement?: True
		Complete basis approximation?: False

		Mode 1:
		--------
		Frequency: 0.500000000000
		Coherent state z: 0.000000000000

		Polarization: 0.27000000 -0.89200000 0.36300000

		Coupling
		sqrt(1/eps V): 0.100000000000
		Bilinear: 0.050000000000
		Quadratic: 0.005000000000

		Peak memory usage during the execution of eT: 45.796064 MB

		Total wall time in eT (s): 6.768
		Total cpu time in eT (s): 64.006

		Calculation end:2025-04-14 11:27:58 UTC +02:00

		- Implementation references:

		eT: https://doi.org/10.1063/5.0004713
		SC-QED-HF: https://doi.org/https://doi.org/10.1038/s41467-022-29003-2
		Cholesky decomposition of ERIs: https://doi.org/10.1063/1.5083802

		eT terminated successfully!