#include <hf.h>

Inheritance diagram for occ::qm::HartreeFock:

Collaboration diagram for occ::qm::HartreeFock:

Public Types
enum class	ResponseMode { Exact , Approximate }
	Operators for a CPHF response: the SCF's own (Exact), or a cheaper stand-in to precondition with (Approximate: RI-J and four-centre exchange; a DFT procedure also coarsens its XC grid). More...
using	COSXGridSchedule = occ::qm::COSXGridSchedule
using	ExchangeOperators = std::vector<std::pair<double, double>>
	Exact-exchange operators (c_t, omega_t) in the energy; HF is {(1, 0)}.

Public Member Functions
	HartreeFock (const AOBasis &basis)
const auto &	aobasis () const
auto	nbf () const
bool	usual_scf_energy () const
void	update_scf_energy (occ::core::EnergyComponents &) const
FockBuildProperties	fock_build_properties () const
bool	have_effective_core_potentials () const
void	set_density_fitting_basis (const std::string &, double auto_aux_threshold=1e-4)
void	set_density_fitting_policy (IntegralEngineDF::Policy policy)
void	set_density_fitting_memory_limit (size_t bytes)
void	set_coulomb_method (CoulombMethod method)
void	set_cosx_exchange (occ::numint::COSXGridLevel level=occ::numint::COSXGridLevel::Grid1)
	COSX exchange on one fixed grid.
void	set_cosx_settings (const occ::qm::cosx::Settings &settings)
void	set_cosx_exchange_scale (double scale)
	The factor the caller applies to this exchange (a global hybrid's exact exchange fraction).
void	set_cosx_grid_schedule (const COSXGridSchedule &schedule={})
bool	advance_scf_grid (double diis_error, bool converged)
	SCF hook: called after each iteration's DIIS step.
bool	scf_fock_approximate () const
	SCF hooks for the frozen grid correction: whether the last Fock build used it (so convergence there is not convergence on the refine grid), and a request that the next build be exact and refresh it.
void	refresh_scf_fock_correction ()
void	set_scf_fock_incremental (bool incremental)
	SCF hook: whether the next Fock build is handed a difference density.
double	incremental_fock_floor () const
	SCF hook: the DIIS error below which difference-density builds stop.
double	final_energy_correction (const MolecularOrbitals &mo)
	SCF hook: called once at convergence.
double	finalize_cosx_grid (const MolecularOrbitals &mo, const ExchangeOperators &operators)
double	cosx_energy_shift_from (occ::numint::COSXGridLevel other, const MolecularOrbitals &mo, const ExchangeOperators &operators={ {1.0, 0.0}})
	COSX exchange energy at mo on the current grid minus that on other, non-self-consistently, leaving the current grid in place.
bool	using_cosx () const
bool	using_density_fitting () const
const IntegralEngine &	integral_engine () const
	The exact-integral engine (one-electron and point-charge integrals).
HartreeFock	with_new_basis (const AOBasis &new_basis) const
	Create a new HartreeFock instance with the same settings but different basis.
void	copy_two_electron_setup_to (HartreeFock &other) const
	Give other (typically the same system at another geometry) this object's two-electron treatment: density fitting (basis rebuilt for other's atoms), Coulomb method and storage policy, and COSX (fixed grid or schedule, and settings).
std::vector< Mat >	factor_response_densities (const std::vector< Mat > &D1, const Mat &C) const
	Factor each response density as Cx C^T + C Cx^T (no virtual-virtual block); throws otherwise.
IntegralEngineDF *	approximate_coulomb_engine () const
	RI-J engine for approximate responses: the SCF's own when it fits J, else one built on def2-universal-jkfit (null if unavailable).
IntegralEngineDF *	exchange_df_engine (double omega) const
	The density-fitting engine for exchange with operator omega (the attenuated twin for omega != 0).
void	set_precision (double precision)
double	integral_precision () const
double	nuclear_point_charge_interaction_energy (const PointChargeList &) const
double	wolf_point_charge_interaction_energy (const PointChargeList &, const std::vector< double > &partial_charges, double alpha, double rc) const
Mat	compute_fock (const MolecularOrbitals &mo, const Mat &Schwarz=Mat()) const
Mat3N	additional_atomic_gradients (const MolecularOrbitals &mo) const
MatTriple	compute_fock_gradient (const MolecularOrbitals &mo, const Mat &Schwarz=Mat()) const
Mat	compute_fock_mixed_basis (const MolecularOrbitals &mo_minbs, const gto::AOBasis &bs, bool is_shell_diagonal)
Mat	compute_fock_from_density (const MolecularOrbitals &mo, const Mat &Schwarz=Mat()) const
	Fock matrix from a density already expressed in this method's own basis.
JKPair	compute_JK (const MolecularOrbitals &mo, const Mat &Schwarz=Mat()) const
JKTriple	compute_JK_gradient (const MolecularOrbitals &mo, const Mat &Schwarz=Mat()) const
std::vector< JKPair >	compute_JK_list (const std::vector< MolecularOrbitals > &mo, const Mat &Schwarz=Mat()) const
Mat	compute_J (const MolecularOrbitals &mo, const Mat &Schwarz=Mat()) const
Mat	compute_K (const MolecularOrbitals &mo, const Mat &Schwarz=Mat()) const
JKPair	coulomb_and_range_separated_exchange (const MolecularOrbitals &mo, double omega, double alpha, double beta, const Mat &Schwarz=Mat())
MatTriple	compute_J_gradient (const MolecularOrbitals &mo, const Mat &Schwarz=Mat()) const
Mat3N	compute_jk_gradient (const MolecularOrbitals &mo, double jf, double kf, const Mat &Schwarz=Mat()) const
	Nuclear gradient of jf * E_J + kf * E_K (E_K the full exact-exchange energy), contracted in the integral loop: 3 x natom, no derivative matrices.
Mat3N	compute_k_gradient_long_range (const MolecularOrbitals &mo, double omega, double kf, const Mat &Schwarz=Mat()) const
	As compute_jk_gradient, exchange only, with the attenuated operator erf(omega r)/r: the gradient of kf * E_K[erf].
std::vector< Mat >	compute_response_fock (const MolecularOrbitals &mo, const std::vector< Mat > &D1, const Mat &Schwarz=Mat()) const
	G[D1] = dF/dD . D1 for each first-order density (same layout as mo.D).
std::vector< Mat >	compute_response_jk (const std::vector< Mat > &D1, double jf, double kf, double omega=0.0, const Mat &Schwarz=Mat(), const MolecularOrbitals *ref=nullptr) const
	jf * 2 J[D1] - kf * K[D1] for each restricted D1; omega != 0 selects the attenuated exchange (then jf must be 0).
std::vector< Mat >	response_occ (const MolecularOrbitals &mo, const std::vector< Mat > &Cx, double jf, const ExchangeOperators &K, const Mat &Schwarz, ResponseMode mode=ResponseMode::Exact) const
	(jf 2 J[D1] - sum_t c_t K_{omega_t}[D1]) Co for D1 = Cx Co^T + Co Cx^T (restricted), or per spin (jf J[D1^a + D1^b] - sum_t c_t K[D1^s]) Co^s (unrestricted).
std::vector< Mat >	compute_response_fock_occ (const MolecularOrbitals &mo, const std::vector< Mat > &Cx, const Mat &Schwarz=Mat()) const
	The CPHF response of HF: G[D1] Co with D1 = Cx Co^T + Co Cx^T.
std::vector< Mat >	compute_response_fock_occ_approx (const MolecularOrbitals &mo, const std::vector< Mat > &Cx, const Mat &Schwarz=Mat()) const
bool	has_approximate_response () const
	Whether the approximate response (density-fitted Coulomb, four-centre exchange) is cheaper than the exact one: only when the exact exchange is COSX, since four-centre exchange costs as much as RI-K.
std::string	analytic_hessian_unsupported (SpinorbitalKind kind) const
	Empty if the analytic Hessian supports this calculation, otherwise why not (the caller falls back to finite differences).
Mat	compute_jk_hessian (const MolecularOrbitals &mo, double jf, const ExchangeOperators &K, const Mat &Schwarz=Mat()) const
	Skeleton Hessian (fixed density) of jf E_J + sum_t c_t E_K[omega_t], with the SCF's operators (four-centre, RI-J, RI-K; four-centre Coulomb and full-range exchange in one pass).
std::vector< Mat >	compute_jk_derivative_fock (const MolecularOrbitals &mo, double jf, const ExchangeOperators &K, const Mat &Schwarz=Mat()) const
	Skeleton Fock derivatives of jf 2J - sum_t c_t K[omega_t] for every nuclear coordinate, as full matrices (unrestricted: per spin, alpha rows over beta rows) or contracted with C_o (cphf::contract_occupied).
std::vector< Mat >	compute_jk_derivative_fock_occ (const MolecularOrbitals &mo, double jf, const ExchangeOperators &K, const Mat &Schwarz=Mat()) const
std::vector< Mat >	compute_exchange_nonvariational_fock_occ (const MolecularOrbitals &mo, const ExchangeOperators &K) const
	d/dR (1/2 dE_K/dD - F_K) C_o at fixed density, F_K = -sum_t c_t K_{omega_t} the SCF's exchange: the COSX Fock is not exactly the energy's density derivative, and the analytic gradient's density response sees the latter.
Mat	compute_one_electron_hessian (const Mat &P, const Mat &Q) const
	sum P h^{xy} - sum Q S^{xy} (3N x 3N), total densities.
void	compute_one_electron_derivative_matrices (std::vector< Mat > &S1, std::vector< Mat > &H1) const
	S^{(x)} and h^{(x)} for every nuclear coordinate (3N each).
Mat	two_electron_hessian (const MolecularOrbitals &mo, const Mat &Schwarz=Mat()) const
	Skeleton two-electron Hessian (fixed density), Coulomb + full exchange.
std::vector< Mat >	two_electron_derivative_fock (const MolecularOrbitals &mo, const Mat &Schwarz=Mat()) const
	Skeleton two-electron Fock derivatives (3N matrices).
std::vector< Mat >	two_electron_derivative_fock_occ (const MolecularOrbitals &mo, const Mat &Schwarz=Mat()) const
	The same contracted with the occupied coefficients (nbf x nocc each).
std::vector< Mat >	nonvariational_fock_derivative_occ (const MolecularOrbitals &mo) const
Mat3N	compute_exchange_gradient (const MolecularOrbitals &mo, double kf, double omega=0.0, const Mat &Schwarz=Mat()) const
	Gradient of kf * E_K for the exchange operator in use: COSX when it is enabled (consistent with the COSX energy), else exact four-centre.
Mat3N	two_electron_gradient (const MolecularOrbitals &mo, const Mat &Schwarz=Mat()) const
	Two-electron part of the HF nuclear gradient (Coulomb + full exchange), with the same exchange approximation as the SCF.
Mat3N	compute_coulomb_gradient (const MolecularOrbitals &mo, const Mat &Schwarz=Mat()) const
	Gradient of E_J for the Coulomb operator in use: RI-J when the SCF's J is density-fitted, else four-centre.
std::vector< Mat >	compute_J_list (const std::vector< MolecularOrbitals > &mo, const Mat &Schwarz=Mat()) const
Mat	compute_kinetic_matrix () const
MatTriple	compute_kinetic_gradient () const
Mat	compute_overlap_matrix () const
Mat	compute_overlap_matrix_for_basis (const occ::gto::AOBasis &basis) const
MatTriple	compute_overlap_gradient () const
Mat	compute_nuclear_attraction_matrix () const
MatTriple	compute_nuclear_attraction_gradient () const
MatTriple	compute_rinv_gradient_for_atom (size_t atom_index) const
Mat	compute_effective_core_potential_matrix () const
Mat3N	compute_ecp_gradient (const MolecularOrbitals &mo) const
	Nuclear gradient of the ECP energy (3 x natoms), zero without ECPs.
Mat	compute_point_charge_interaction_matrix (const PointChargeList &point_charges, double alpha=1e16) const
Mat	compute_wolf_interaction_matrix (const PointChargeList &point_charges, const std::vector< double > &partial_charges, double alpha, double rc) const
Mat3N	electronic_electric_field_contribution (const MolecularOrbitals &mo, const Mat3N &) const
Vec	electronic_electric_potential_contribution (const MolecularOrbitals &mo, const Mat3N &) const
Mat	compute_schwarz_ints () const
void	update_core_hamiltonian (const MolecularOrbitals &mo, Mat &H)
template<int order>
occ::core::Multipole< order >	compute_electronic_multipoles (const MolecularOrbitals &mo, const Vec3 &o={0.0, 0.0, 0.0}) const
template<unsigned int order = 1>
auto	compute_nuclear_multipoles (const Vec3 &o={0.0, 0.0, 0.0}) const
template<int order>
auto	compute_multipoles (const MolecularOrbitals &mo, const Vec3 &o={0.0, 0.0, 0.0}) const
Mat	compute_K_long_range (const MolecularOrbitals &mo, double omega, const Mat &Schwarz=Mat()) const
	Exchange built with the attenuated operator erf(omega r)/r.
MatTriple	compute_K_gradient_long_range (const MolecularOrbitals &mo, double omega, const Mat &Schwarz=Mat()) const
	Exchange gradient with the attenuated operator, as above.
std::string	name () const
Public Member Functions inherited from occ::qm::SCFMethodBase
	SCFMethodBase (const std::vector< core::Atom > &)
const auto &	atoms () const
int	system_charge () const
int	total_electrons () const
int	active_electrons () const
const auto &	frozen_electrons () const
Vec3	center_of_mass () const
void	set_system_charge (int charge)
double	nuclear_repulsion_energy () const
Mat3N	nuclear_repulsion_gradient () const
Vec	nuclear_electric_potential_contribution (const Mat3N &) const
Mat3N	nuclear_electric_field_contribution (const Mat3N &) const
void	set_frozen_electrons (const std::vector< int > &)

Additional Inherited Members
Protected Member Functions inherited from occ::qm::SCFMethodBase
void	update_electron_count ()
Protected Attributes inherited from occ::qm::SCFMethodBase
int	m_charge {0}
int	m_num_electrons {0}
int	m_num_frozen {0}
std::vector< occ::core::Atom >	m_atoms
std::vector< int >	m_frozen_electrons

Member Typedef Documentation

◆ COSXGridSchedule

using occ::qm::HartreeFock::COSXGridSchedule = occ::qm::COSXGridSchedule

◆ ExchangeOperators

using occ::qm::HartreeFock::ExchangeOperators = std::vector<std::pair<double, double>>

Exact-exchange operators (c_t, omega_t) in the energy; HF is {(1, 0)}.

Member Enumeration Documentation

◆ ResponseMode

enum class occ::qm::HartreeFock::ResponseMode

strong

Operators for a CPHF response: the SCF's own (Exact), or a cheaper stand-in to precondition with (Approximate: RI-J and four-centre exchange; a DFT procedure also coarsens its XC grid).

Enumerator
Exact
Approximate

Constructor & Destructor Documentation

◆ HartreeFock()

occ::qm::HartreeFock::HartreeFock ( const AOBasis & basis )

Member Function Documentation

◆ additional_atomic_gradients()

Mat3N occ::qm::HartreeFock::additional_atomic_gradients ( const MolecularOrbitals & mo ) const

inline

◆ advance_scf_grid()

bool occ::qm::HartreeFock::advance_scf_grid	(	double	diis_error,
		bool	converged )

SCF hook: called after each iteration's DIIS step.

Returns true when the procedure switched to a finer COSX grid, in which case the SCF must rebuild the Fock matrix in full and keep iterating.

◆ analytic_hessian_unsupported()

std::string occ::qm::HartreeFock::analytic_hessian_unsupported ( SpinorbitalKind kind ) const

inline

Empty if the analytic Hessian supports this calculation, otherwise why not (the caller falls back to finite differences).

◆ aobasis()

const auto & occ::qm::HartreeFock::aobasis ( ) const

inline

◆ approximate_coulomb_engine()

IntegralEngineDF * occ::qm::HartreeFock::approximate_coulomb_engine ( ) const

RI-J engine for approximate responses: the SCF's own when it fits J, else one built on def2-universal-jkfit (null if unavailable).

◆ compute_coulomb_gradient()

Mat3N occ::qm::HartreeFock::compute_coulomb_gradient	(	const MolecularOrbitals &	mo,
		const Mat &	Schwarz = Mat() ) const

inline

Gradient of E_J for the Coulomb operator in use: RI-J when the SCF's J is density-fitted, else four-centre.

◆ compute_ecp_gradient()

Mat3N occ::qm::HartreeFock::compute_ecp_gradient ( const MolecularOrbitals & mo ) const

inline

Nuclear gradient of the ECP energy (3 x natoms), zero without ECPs.

Contracted with mo's density; the caller applies occ's factor of two. The ECP operator is spin-independent, so open-shell densities are contracted as the sum of their spin blocks. Handing the kernel the stacked 2n x n mo.D would silently read only the alpha block, since it indexes D.block(bf0, bf1, ...).

◆ compute_effective_core_potential_matrix()

Mat occ::qm::HartreeFock::compute_effective_core_potential_matrix ( ) const

◆ compute_electronic_multipoles()

template<int order>

occ::core::Multipole< order > occ::qm::HartreeFock::compute_electronic_multipoles	(	const MolecularOrbitals &	mo,
		const Vec3 &	o = {0.0, 0.0, 0.0} ) const

inline

◆ compute_exchange_gradient()

Mat3N occ::qm::HartreeFock::compute_exchange_gradient	(	const MolecularOrbitals &	mo,
		double	kf,
		double	omega = 0.0,
		const Mat &	Schwarz = Mat() ) const

Gradient of kf * E_K for the exchange operator in use: COSX when it is enabled (consistent with the COSX energy), else exact four-centre.

omega != 0 selects erf(omega r)/r.

◆ compute_exchange_nonvariational_fock_occ()

std::vector< Mat > occ::qm::HartreeFock::compute_exchange_nonvariational_fock_occ	(	const MolecularOrbitals &	mo,
		const ExchangeOperators &	K ) const

d/dR (1/2 dE_K/dD - F_K) C_o at fixed density, F_K = -sum_t c_t K_{omega_t} the SCF's exchange: the COSX Fock is not exactly the energy's density derivative, and the analytic gradient's density response sees the latter.

Empty when they coincide (not COSX).

◆ compute_fock()

Mat occ::qm::HartreeFock::compute_fock	(	const MolecularOrbitals &	mo,
		const Mat &	Schwarz = Mat() ) const

◆ compute_fock_from_density()

Mat occ::qm::HartreeFock::compute_fock_from_density	(	const MolecularOrbitals &	mo,
		const Mat &	Schwarz = Mat() ) const

inline

Fock matrix from a density already expressed in this method's own basis.

The conventional four-centre build, which reads mo.D and screens on it as well as on Schwarz. Density fitting and COSX cannot serve here: both build exchange from the occupied coefficients, and a guess has a density before it has any orbitals.

Distinct from compute_fock_mixed_basis, which exists to project a density out of a different basis. Handing that function this method's own basis makes it duplicate every shell as auxiliary and run the full four-index loop unscreened – on a 566-function system that cost 256 s against 59 s for the whole rest of an SCF iteration.

◆ compute_fock_gradient()

MatTriple occ::qm::HartreeFock::compute_fock_gradient	(	const MolecularOrbitals &	mo,
		const Mat &	Schwarz = Mat() ) const

◆ compute_fock_mixed_basis()

Mat occ::qm::HartreeFock::compute_fock_mixed_basis	(	const MolecularOrbitals &	mo_minbs,
		const gto::AOBasis &	bs,
		bool	is_shell_diagonal )

◆ compute_J()

Mat occ::qm::HartreeFock::compute_J	(	const MolecularOrbitals &	mo,
		const Mat &	Schwarz = Mat() ) const

◆ compute_J_gradient()

MatTriple occ::qm::HartreeFock::compute_J_gradient	(	const MolecularOrbitals &	mo,
		const Mat &	Schwarz = Mat() ) const

◆ compute_J_list()

std::vector< Mat > occ::qm::HartreeFock::compute_J_list	(	const std::vector< MolecularOrbitals > &	mo,
		const Mat &	Schwarz = Mat() ) const

◆ compute_JK()

JKPair occ::qm::HartreeFock::compute_JK	(	const MolecularOrbitals &	mo,
		const Mat &	Schwarz = Mat() ) const

◆ compute_jk_derivative_fock()

std::vector< Mat > occ::qm::HartreeFock::compute_jk_derivative_fock	(	const MolecularOrbitals &	mo,
		double	jf,
		const ExchangeOperators &	K,
		const Mat &	Schwarz = Mat() ) const

Skeleton Fock derivatives of jf 2J - sum_t c_t K[omega_t] for every nuclear coordinate, as full matrices (unrestricted: per spin, alpha rows over beta rows) or contracted with C_o (cphf::contract_occupied).

◆ compute_jk_derivative_fock_occ()

std::vector< Mat > occ::qm::HartreeFock::compute_jk_derivative_fock_occ	(	const MolecularOrbitals &	mo,
		double	jf,
		const ExchangeOperators &	K,
		const Mat &	Schwarz = Mat() ) const

◆ compute_JK_gradient()

JKTriple occ::qm::HartreeFock::compute_JK_gradient	(	const MolecularOrbitals &	mo,
		const Mat &	Schwarz = Mat() ) const

◆ compute_jk_gradient()

Mat3N occ::qm::HartreeFock::compute_jk_gradient	(	const MolecularOrbitals &	mo,
		double	jf,
		double	kf,
		const Mat &	Schwarz = Mat() ) const

Nuclear gradient of jf * E_J + kf * E_K (E_K the full exact-exchange energy), contracted in the integral loop: 3 x natom, no derivative matrices.

Always the conventional four-centre engine.

◆ compute_jk_hessian()

Mat occ::qm::HartreeFock::compute_jk_hessian	(	const MolecularOrbitals &	mo,
		double	jf,
		const ExchangeOperators &	K,
		const Mat &	Schwarz = Mat() ) const

Skeleton Hessian (fixed density) of jf E_J + sum_t c_t E_K[omega_t], with the SCF's operators (four-centre, RI-J, RI-K; four-centre Coulomb and full-range exchange in one pass).

◆ compute_JK_list()

std::vector< JKPair > occ::qm::HartreeFock::compute_JK_list	(	const std::vector< MolecularOrbitals > &	mo,
		const Mat &	Schwarz = Mat() ) const

◆ compute_K()

Mat occ::qm::HartreeFock::compute_K	(	const MolecularOrbitals &	mo,
		const Mat &	Schwarz = Mat() ) const

◆ compute_K_gradient_long_range()

MatTriple occ::qm::HartreeFock::compute_K_gradient_long_range	(	const MolecularOrbitals &	mo,
		double	omega,
		const Mat &	Schwarz = Mat() ) const

Exchange gradient with the attenuated operator, as above.

◆ compute_k_gradient_long_range()

Mat3N occ::qm::HartreeFock::compute_k_gradient_long_range	(	const MolecularOrbitals &	mo,
		double	omega,
		double	kf,
		const Mat &	Schwarz = Mat() ) const

As compute_jk_gradient, exchange only, with the attenuated operator erf(omega r)/r: the gradient of kf * E_K[erf].

◆ compute_K_long_range()

Mat occ::qm::HartreeFock::compute_K_long_range	(	const MolecularOrbitals &	mo,
		double	omega,
		const Mat &	Schwarz = Mat() ) const

Exchange built with the attenuated operator erf(omega r)/r.

The attenuated operator gets its own engines, fixed to it for the life of the calculation, rather than being produced by toggling omega on the shared ones and toggling it back. Omega is constant for a calculation – it comes from the functional – so the only thing the toggling ever bought was letting one engine serve two operators, and it cost exception safety, const-correctness, and the ability to cache anything that belongs to an operator rather than to a basis.

COSX is the exception and takes omega as a plain argument: nothing in it is cached per operator, so a second grid and shell-pair map would be pure duplication.

◆ compute_kinetic_gradient()

MatTriple occ::qm::HartreeFock::compute_kinetic_gradient ( ) const

◆ compute_kinetic_matrix()

Mat occ::qm::HartreeFock::compute_kinetic_matrix ( ) const

◆ compute_multipoles()

template<int order>

auto occ::qm::HartreeFock::compute_multipoles	(	const MolecularOrbitals &	mo,
		const Vec3 &	o = {0.0, 0.0, 0.0} ) const

inline

◆ compute_nuclear_attraction_gradient()

MatTriple occ::qm::HartreeFock::compute_nuclear_attraction_gradient ( ) const

◆ compute_nuclear_attraction_matrix()

Mat occ::qm::HartreeFock::compute_nuclear_attraction_matrix ( ) const

◆ compute_nuclear_multipoles()

template<unsigned int order = 1>

auto occ::qm::HartreeFock::compute_nuclear_multipoles ( const Vec3 & o = {0.0, 0.0, 0.0} ) const

inline

◆ compute_one_electron_derivative_matrices()

void occ::qm::HartreeFock::compute_one_electron_derivative_matrices	(	std::vector< Mat > &	S1,
		std::vector< Mat > &	H1 ) const

inline

S^{(x)} and h^{(x)} for every nuclear coordinate (3N each).

◆ compute_one_electron_hessian()

Mat occ::qm::HartreeFock::compute_one_electron_hessian	(	const Mat &	P,
		const Mat &	Q ) const

inline

sum P h^{xy} - sum Q S^{xy} (3N x 3N), total densities.

◆ compute_overlap_gradient()

MatTriple occ::qm::HartreeFock::compute_overlap_gradient ( ) const

◆ compute_overlap_matrix()

Mat occ::qm::HartreeFock::compute_overlap_matrix ( ) const

◆ compute_overlap_matrix_for_basis()

Mat occ::qm::HartreeFock::compute_overlap_matrix_for_basis ( const occ::gto::AOBasis & basis ) const

◆ compute_point_charge_interaction_matrix()

Mat occ::qm::HartreeFock::compute_point_charge_interaction_matrix	(	const PointChargeList &	point_charges,
		double	alpha = 1e16 ) const

◆ compute_response_fock()

std::vector< Mat > occ::qm::HartreeFock::compute_response_fock	(	const MolecularOrbitals &	mo,
		const std::vector< Mat > &	D1,
		const Mat &	Schwarz = Mat() ) const

G[D1] = dF/dD . D1 for each first-order density (same layout as mo.D).

◆ compute_response_fock_occ()

std::vector< Mat > occ::qm::HartreeFock::compute_response_fock_occ	(	const MolecularOrbitals &	mo,
		const std::vector< Mat > &	Cx,
		const Mat &	Schwarz = Mat() ) const

inline

The CPHF response of HF: G[D1] Co with D1 = Cx Co^T + Co Cx^T.

◆ compute_response_fock_occ_approx()

std::vector< Mat > occ::qm::HartreeFock::compute_response_fock_occ_approx	(	const MolecularOrbitals &	mo,
		const std::vector< Mat > &	Cx,
		const Mat &	Schwarz = Mat() ) const

inline

◆ compute_response_jk()

std::vector< Mat > occ::qm::HartreeFock::compute_response_jk	(	const std::vector< Mat > &	D1,
		double	jf,
		double	kf,
		double	omega = 0.0,
		const Mat &	Schwarz = Mat(),
		const MolecularOrbitals *	ref = nullptr ) const

jf * 2 J[D1] - kf * K[D1] for each restricted D1; omega != 0 selects the attenuated exchange (then jf must be 0).

ref (the reference orbitals) is needed for density-fitted exchange.

◆ compute_rinv_gradient_for_atom()

MatTriple occ::qm::HartreeFock::compute_rinv_gradient_for_atom ( size_t atom_index ) const

◆ compute_schwarz_ints()

Mat occ::qm::HartreeFock::compute_schwarz_ints ( ) const

◆ compute_wolf_interaction_matrix()

Mat occ::qm::HartreeFock::compute_wolf_interaction_matrix	(	const PointChargeList &	point_charges,
		const std::vector< double > &	partial_charges,
		double	alpha,
		double	rc ) const

◆ copy_two_electron_setup_to()

void occ::qm::HartreeFock::copy_two_electron_setup_to ( HartreeFock & other ) const

Give other (typically the same system at another geometry) this object's two-electron treatment: density fitting (basis rebuilt for other's atoms), Coulomb method and storage policy, and COSX (fixed grid or schedule, and settings).

Finite-difference derivatives need this to stay on one energy surface.

◆ cosx_energy_shift_from()

double occ::qm::HartreeFock::cosx_energy_shift_from	(	occ::numint::COSXGridLevel	other,
		const MolecularOrbitals &	mo,
		const ExchangeOperators &	operators = { {1.0, 0.0}} )

COSX exchange energy at mo on the current grid minus that on other, non-self-consistently, leaving the current grid in place.

Used to put energies from SCFs on different grids on one surface.

◆ coulomb_and_range_separated_exchange()

JKPair occ::qm::HartreeFock::coulomb_and_range_separated_exchange	(	const MolecularOrbitals &	mo,
		double	omega,
		double	alpha,
		double	beta,
		const Mat &	Schwarz = Mat() )

◆ electronic_electric_field_contribution()

Mat3N occ::qm::HartreeFock::electronic_electric_field_contribution	(	const MolecularOrbitals &	mo,
		const Mat3N &	) const

◆ electronic_electric_potential_contribution()

Vec occ::qm::HartreeFock::electronic_electric_potential_contribution	(	const MolecularOrbitals &	mo,
		const Mat3N &	) const

◆ exchange_df_engine()

IntegralEngineDF * occ::qm::HartreeFock::exchange_df_engine ( double omega ) const

The density-fitting engine for exchange with operator omega (the attenuated twin for omega != 0).

◆ factor_response_densities()

std::vector< Mat > occ::qm::HartreeFock::factor_response_densities	(	const std::vector< Mat > &	D1,
		const Mat &	C ) const

Factor each response density as Cx C^T + C Cx^T (no virtual-virtual block); throws otherwise.

◆ final_energy_correction()

double occ::qm::HartreeFock::final_energy_correction ( const MolecularOrbitals & mo )

SCF hook: called once at convergence.

With a COSX schedule, moves to the final grid and returns the change in the exact-exchange energy, -sum_t c_t [tr(D K_t,final) - tr(D K_t,current)] for the operators (c_t, omega_t) given (default: full HF exchange).

◆ finalize_cosx_grid()

double occ::qm::HartreeFock::finalize_cosx_grid	(	const MolecularOrbitals &	mo,
		const ExchangeOperators &	operators )

◆ fock_build_properties()

FockBuildProperties occ::qm::HartreeFock::fock_build_properties ( ) const

inline

◆ has_approximate_response()

bool occ::qm::HartreeFock::has_approximate_response ( ) const

inline

Whether the approximate response (density-fitted Coulomb, four-centre exchange) is cheaper than the exact one: only when the exact exchange is COSX, since four-centre exchange costs as much as RI-K.

◆ have_effective_core_potentials()

bool occ::qm::HartreeFock::have_effective_core_potentials ( ) const

inline

◆ incremental_fock_floor()

double occ::qm::HartreeFock::incremental_fock_floor ( ) const

inline

SCF hook: the DIIS error below which difference-density builds stop.

The COSX charge x density screen is absolute, so each difference build drops a different set of shell pairs and the accumulated exchange carries their error; below this the iterations are full builds, so the SCF converges onto the full build's own fixed point.

◆ integral_engine()

const IntegralEngine & occ::qm::HartreeFock::integral_engine ( ) const

inline

The exact-integral engine (one-electron and point-charge integrals).

◆ integral_precision()

double occ::qm::HartreeFock::integral_precision ( ) const

inline

◆ name()

std::string occ::qm::HartreeFock::name ( ) const

inline

◆ nbf()

auto occ::qm::HartreeFock::nbf ( ) const

inline

◆ nonvariational_fock_derivative_occ()

std::vector< Mat > occ::qm::HartreeFock::nonvariational_fock_derivative_occ ( const MolecularOrbitals & mo ) const

inline

◆ nuclear_point_charge_interaction_energy()

double occ::qm::HartreeFock::nuclear_point_charge_interaction_energy ( const PointChargeList & ) const

◆ refresh_scf_fock_correction()

void occ::qm::HartreeFock::refresh_scf_fock_correction ( )

inline

◆ response_occ()

std::vector< Mat > occ::qm::HartreeFock::response_occ	(	const MolecularOrbitals &	mo,
		const std::vector< Mat > &	Cx,
		double	jf,
		const ExchangeOperators &	K,
		const Mat &	Schwarz,
		ResponseMode	mode = ResponseMode::Exact ) const

(jf 2 J[D1] - sum_t c_t K_{omega_t}[D1]) Co for D1 = Cx Co^T + Co Cx^T (restricted), or per spin (jf J[D1^a + D1^b] - sum_t c_t K[D1^s]) Co^s (unrestricted).

Four-centre Coulomb and full-range exchange share one integral pass when both are four-centre.

◆ scf_fock_approximate()

bool occ::qm::HartreeFock::scf_fock_approximate ( ) const

inline

SCF hooks for the frozen grid correction: whether the last Fock build used it (so convergence there is not convergence on the refine grid), and a request that the next build be exact and refresh it.

◆ set_cosx_exchange()

void occ::qm::HartreeFock::set_cosx_exchange ( occ::numint::COSXGridLevel level = occ::numint::COSXGridLevel::Grid1 )

COSX exchange on one fixed grid.

◆ set_cosx_exchange_scale()

void occ::qm::HartreeFock::set_cosx_exchange_scale ( double scale )

The factor the caller applies to this exchange (a global hybrid's exact exchange fraction).

The COSX shell-pair screen is loosened by it, so the absolute screening error in the Fock matrix stays that of HF.

◆ set_cosx_grid_schedule()

void occ::qm::HartreeFock::set_cosx_grid_schedule ( const COSXGridSchedule & schedule = {} )

◆ set_cosx_settings()

void occ::qm::HartreeFock::set_cosx_settings ( const occ::qm::cosx::Settings & settings )

◆ set_coulomb_method()

void occ::qm::HartreeFock::set_coulomb_method ( CoulombMethod method )

◆ set_density_fitting_basis()

void occ::qm::HartreeFock::set_density_fitting_basis	(	const std::string &	,
		double	auto_aux_threshold = 1e-4 )

◆ set_density_fitting_memory_limit()

void occ::qm::HartreeFock::set_density_fitting_memory_limit ( size_t bytes )

◆ set_density_fitting_policy()

void occ::qm::HartreeFock::set_density_fitting_policy ( IntegralEngineDF::Policy policy )

◆ set_precision()

void occ::qm::HartreeFock::set_precision ( double precision )

inline

◆ set_scf_fock_incremental()

void occ::qm::HartreeFock::set_scf_fock_incremental ( bool incremental )

SCF hook: whether the next Fock build is handed a difference density.

An incremental build leaves out the frozen grid correction (it is already in the accumulated Fock matrix) and must not refresh it.

◆ two_electron_derivative_fock()

std::vector< Mat > occ::qm::HartreeFock::two_electron_derivative_fock	(	const MolecularOrbitals &	mo,
		const Mat &	Schwarz = Mat() ) const

inline

Skeleton two-electron Fock derivatives (3N matrices).

◆ two_electron_derivative_fock_occ()

std::vector< Mat > occ::qm::HartreeFock::two_electron_derivative_fock_occ	(	const MolecularOrbitals &	mo,
		const Mat &	Schwarz = Mat() ) const

inline

The same contracted with the occupied coefficients (nbf x nocc each).

◆ two_electron_gradient()

Mat3N occ::qm::HartreeFock::two_electron_gradient	(	const MolecularOrbitals &	mo,
		const Mat &	Schwarz = Mat() ) const

inline

Two-electron part of the HF nuclear gradient (Coulomb + full exchange), with the same exchange approximation as the SCF.

◆ two_electron_hessian()

Mat occ::qm::HartreeFock::two_electron_hessian	(	const MolecularOrbitals &	mo,
		const Mat &	Schwarz = Mat() ) const

inline

Skeleton two-electron Hessian (fixed density), Coulomb + full exchange.

◆ update_core_hamiltonian()

void occ::qm::HartreeFock::update_core_hamiltonian	(	const MolecularOrbitals &	mo,
		Mat &	H )

inline

◆ update_scf_energy()

void occ::qm::HartreeFock::update_scf_energy ( occ::core::EnergyComponents & ) const

inline

◆ using_cosx()

bool occ::qm::HartreeFock::using_cosx ( ) const

inline

◆ using_density_fitting()

bool occ::qm::HartreeFock::using_density_fitting ( ) const

inline

◆ usual_scf_energy()

bool occ::qm::HartreeFock::usual_scf_energy ( ) const

inline

◆ with_new_basis()

HartreeFock occ::qm::HartreeFock::with_new_basis ( const AOBasis & new_basis ) const

Create a new HartreeFock instance with the same settings but different basis.

Parameters

new_basis The new basis set to use

Returns: New HartreeFock instance

◆ wolf_point_charge_interaction_energy()

double occ::qm::HartreeFock::wolf_point_charge_interaction_energy	(	const PointChargeList &	,
		const std::vector< double > &	partial_charges,
		double	alpha,
		double	rc ) const

The documentation for this class was generated from the following file:

/home/runner/work/occ/occ/include/occ/qm/hf.h

Public Types

Public Member Functions

Additional Inherited Members

Member Typedef Documentation

◆ COSXGridSchedule

◆ ExchangeOperators

Member Enumeration Documentation

◆ ResponseMode

Constructor & Destructor Documentation

◆ HartreeFock()

Member Function Documentation

◆ additional_atomic_gradients()

◆ advance_scf_grid()

◆ analytic_hessian_unsupported()

◆ aobasis()

◆ approximate_coulomb_engine()

◆ compute_coulomb_gradient()

◆ compute_ecp_gradient()

◆ compute_effective_core_potential_matrix()

◆ compute_electronic_multipoles()

◆ compute_exchange_gradient()

◆ compute_exchange_nonvariational_fock_occ()

◆ compute_fock()

◆ compute_fock_from_density()

◆ compute_fock_gradient()

◆ compute_fock_mixed_basis()

◆ compute_J()

◆ compute_J_gradient()

◆ compute_J_list()

◆ compute_JK()

◆ compute_jk_derivative_fock()

◆ compute_jk_derivative_fock_occ()

◆ compute_JK_gradient()

◆ compute_jk_gradient()

◆ compute_jk_hessian()

◆ compute_JK_list()

◆ compute_K()

◆ compute_K_gradient_long_range()

◆ compute_k_gradient_long_range()

◆ compute_K_long_range()

◆ compute_kinetic_gradient()

◆ compute_kinetic_matrix()

◆ compute_multipoles()

◆ compute_nuclear_attraction_gradient()

◆ compute_nuclear_attraction_matrix()

◆ compute_nuclear_multipoles()

◆ compute_one_electron_derivative_matrices()

◆ compute_one_electron_hessian()

◆ compute_overlap_gradient()

◆ compute_overlap_matrix()

◆ compute_overlap_matrix_for_basis()

◆ compute_point_charge_interaction_matrix()

◆ compute_response_fock()

◆ compute_response_fock_occ()

◆ compute_response_fock_occ_approx()

◆ compute_response_jk()

◆ compute_rinv_gradient_for_atom()

◆ compute_schwarz_ints()

◆ compute_wolf_interaction_matrix()

◆ copy_two_electron_setup_to()

◆ cosx_energy_shift_from()

◆ coulomb_and_range_separated_exchange()

◆ electronic_electric_field_contribution()

◆ electronic_electric_potential_contribution()

◆ exchange_df_engine()

◆ factor_response_densities()

◆ final_energy_correction()

◆ finalize_cosx_grid()

◆ fock_build_properties()

◆ has_approximate_response()

◆ have_effective_core_potentials()

◆ incremental_fock_floor()

◆ integral_engine()

◆ integral_precision()

◆ name()

◆ nbf()

◆ nonvariational_fock_derivative_occ()

◆ nuclear_point_charge_interaction_energy()

◆ refresh_scf_fock_correction()

◆ response_occ()