Evaluates electronic coupling elements. More...

#include <bsecoupling.h>

Inheritance diagram for votca::xtp::BSECoupling:

Collaboration diagram for votca::xtp::BSECoupling:

[legend]

Classes
struct	Diagnostics
	Diagnostic quantities for assessing whether CT downfolding is safe. More...

Public Member Functions
void	Initialize (tools::Property &options) override
std::string	Identify () const
void	Addoutput (tools::Property &type_summary, const Orbitals &orbitalsA, const Orbitals &orbitalsB) const override
void	CalculateCouplings (const Orbitals &orbitalsA, const Orbitals &orbitalsB, const Orbitals &orbitalsAB) override
	evaluates electronic couplings
Public Member Functions inherited from votca::xtp::CouplingBase
void	setLogger (Logger *pLog)

Private Member Functions
void	WriteToProperty (tools::Property &summary, const QMState &stateA, const QMState &stateB) const
double	getSingletCouplingElement (Index levelA, Index levelB, Index methodindex) const
double	getTripletCouplingElement (Index levelA, Index levelB, Index methodindex) const
Eigen::MatrixXd	SetupCTStates (Index bseA_vtotal, Index bseB_vtotal, Index bseAB_vtotal, Index bseAB_ctotal, const Eigen::MatrixXd &A_AB, const Eigen::MatrixXd &B_AB) const
Eigen::MatrixXd	ProjectFrenkelExcitons (const Eigen::MatrixXd &BSE_Coeffs, const Eigen::MatrixXd &X_AB, Index bseX_vtotal, Index bseX_ctotal, Index bseAB_vtotal, Index bseAB_ctotal) const
template<class BSE_OPERATOR>
std::array< Eigen::MatrixXd, 2 >	ProjectExcitons (Eigen::MatrixXd &FE_AB, Eigen::MatrixXd &CTStates, BSE_OPERATOR H, Eigen::MatrixXd &J_dimer_out, Eigen::MatrixXd &S_dimer_out, Diagnostics &diag_out) const
	Compute J_pert and J_diag, and store raw J_dimer/S_dimer and diagnostics for later output.
template<class BSE_OPERATOR>
Eigen::MatrixXd	CalcJ_dimer (BSE_OPERATOR &H, Eigen::MatrixXd &projection, Eigen::MatrixXd &J_dimer_out, Eigen::MatrixXd &S_dimer_out) const
	Form J_dimer and S_dimer from the projection, then Lowdin orthogonalize to produce J_ortho.
Eigen::MatrixXd	OrthogonalizeCTs (Eigen::MatrixXd &FE_AB, Eigen::MatrixXd &CTStates) const
	Merge FE and CT projection vectors into a single projection matrix without pre-orthogonalization.
Eigen::MatrixXd	Fulldiag (const Eigen::MatrixXd &J_dimer) const
Eigen::MatrixXd	Perturbation (const Eigen::MatrixXd &J_dimer) const
Diagnostics	ComputeDiagnostics (const Eigen::MatrixXd &J_dimer, const Eigen::MatrixXd &J_pert, const Eigen::MatrixXd &J_diag) const
	Compute diagnostics from raw J_dimer and the two effective coupling matrices.

Static Private Member Functions
static void	WriteMatrixToProperty (tools::Property &prop, const std::string &name, const Eigen::MatrixXd &mat, double conversion=1.0)
	Write an Eigen matrix as rows of space-separated values into an XML property node. Each row becomes an attribute "row_N".

Private Attributes
std::array< Eigen::MatrixXd, 2 >	JAB_singlet
std::array< Eigen::MatrixXd, 2 >	JAB_triplet
Eigen::MatrixXd	J_dimer_singlet_
Eigen::MatrixXd	S_dimer_singlet_
Eigen::MatrixXd	J_dimer_triplet_
Eigen::MatrixXd	S_dimer_triplet_
Diagnostics	diag_singlet_
Diagnostics	diag_triplet_
Eigen::VectorXd	monomerA_energies_singlet_
Eigen::VectorXd	monomerB_energies_singlet_
Eigen::VectorXd	monomerA_energies_triplet_
Eigen::VectorXd	monomerB_energies_triplet_
bool	doTriplets_
bool	doSinglets_
bool	output_perturbation_
bool	output_tb_ = false
Index	levA_
Index	levB_
Index	occA_
Index	unoccA_
Index	occB_
Index	unoccB_

Additional Inherited Members
Protected Member Functions inherited from votca::xtp::CouplingBase
void	CheckAtomCoordinates (const Orbitals &orbitalsA, const Orbitals &orbitalsB, const Orbitals &orbitalsAB) const
Eigen::MatrixXd	CalculateOverlapMatrix (const Orbitals &orbitalsAB) const
Protected Attributes inherited from votca::xtp::CouplingBase
Logger *	pLog_

Detailed Description

Evaluates electronic coupling elements.

J. Wehner,B. Baumeier, JCTC DOI: 10.1021/acs.jctc.6b00935

Definition at line 39 of file bsecoupling.h.

Member Function Documentation

◆ Addoutput()

void votca::xtp::BSECoupling::Addoutput	(	tools::Property &	type_summary,
		const Orbitals &	orbitalsA,
		const Orbitals &	orbitalsB ) const

overridevirtual

Implements votca::xtp::CouplingBase.

Definition at line 128 of file bsecoupling.cc.

◆ CalcJ_dimer()

template<class BSE_OPERATOR>

Eigen::MatrixXd votca::xtp::BSECoupling::CalcJ_dimer	(	BSE_OPERATOR &	H,
		Eigen::MatrixXd &	projection,
		Eigen::MatrixXd &	J_dimer_out,
		Eigen::MatrixXd &	S_dimer_out ) const

private

Form J_dimer and S_dimer from the projection, then Lowdin orthogonalize to produce J_ortho.

Parameters

H	BSE Hamiltonian operator
projection	merged FE+CT projection matrix (consumed)
J_dimer_out	raw Hamiltonian matrix before Lowdin [out]
S_dimer_out	raw overlap matrix before Lowdin [out]

Returns: Lowdin-orthogonalized Hamiltonian J_ortho

Definition at line 690 of file bsecoupling.cc.

◆ CalculateCouplings()

void votca::xtp::BSECoupling::CalculateCouplings	(	const Orbitals &	orbitalsA,
		const Orbitals &	orbitalsB,
		const Orbitals &	orbitalsAB )

overridevirtual

evaluates electronic couplings

Parameters

orbitalsA	molecular orbitals of molecule A
orbitalsB	molecular orbitals of molecule B
orbitalsAB	molecular orbitals of the dimer AB

Implements votca::xtp::CouplingBase.

Definition at line 355 of file bsecoupling.cc.

◆ ComputeDiagnostics()

BSECoupling::Diagnostics votca::xtp::BSECoupling::ComputeDiagnostics	(	const Eigen::MatrixXd &	J_dimer,
		const Eigen::MatrixXd &	J_pert,
		const Eigen::MatrixXd &	J_diag ) const

private

Compute diagnostics from raw J_dimer and the two effective coupling matrices.

Parameters

J_dimer	raw (pre-Lowdin) Hamiltonian in FE+CT basis
J_pert	effective couplings from perturbation theory
J_diag	effective couplings from reduction method

Returns: populated Diagnostics struct

Definition at line 747 of file bsecoupling.cc.

◆ Fulldiag()

Eigen::MatrixXd votca::xtp::BSECoupling::Fulldiag ( const Eigen::MatrixXd & J_dimer ) const

private

Definition at line 912 of file bsecoupling.cc.

◆ getSingletCouplingElement()

double votca::xtp::BSECoupling::getSingletCouplingElement	(	Index	levelA,
		Index	levelB,
		Index	methodindex ) const

private

Definition at line 260 of file bsecoupling.cc.

◆ getTripletCouplingElement()

double votca::xtp::BSECoupling::getTripletCouplingElement	(	Index	levelA,
		Index	levelB,
		Index	methodindex ) const

private

Definition at line 266 of file bsecoupling.cc.

◆ Identify()

std::string votca::xtp::BSECoupling::Identify ( ) const

inline

Definition at line 42 of file bsecoupling.h.

◆ Initialize()

void votca::xtp::BSECoupling::Initialize ( tools::Property & options )

overridevirtual

Implements votca::xtp::CouplingBase.

Definition at line 38 of file bsecoupling.cc.

◆ OrthogonalizeCTs()

Eigen::MatrixXd votca::xtp::BSECoupling::OrthogonalizeCTs	(	Eigen::MatrixXd &	FE_AB,
		Eigen::MatrixXd &	CTStates ) const

private

Merge FE and CT projection vectors into a single projection matrix without pre-orthogonalization.

The non-orthogonality between FE and CT states is handled correctly downstream by the joint Lowdin in CalcJ_dimer (for the reduction method) or by the generalized eigenvalue problem / SRG (for TB use of J_dimer and S_dimer directly).

Pre-orthogonalizing CT states against FE states (previous behaviour) used the incorrect projector P = F*F^T, which is only exact when FE_AB columns are orthonormal. This introduced a systematic error that grows with the number of CT states included. The function name is retained for interface compatibility but the orthogonalization step has been removed.

Definition at line 645 of file bsecoupling.cc.

◆ Perturbation()

Eigen::MatrixXd votca::xtp::BSECoupling::Perturbation ( const Eigen::MatrixXd & J_dimer ) const

private

Definition at line 838 of file bsecoupling.cc.

◆ ProjectExcitons()

template<class BSE_OPERATOR>

std::array< Eigen::MatrixXd, 2 > votca::xtp::BSECoupling::ProjectExcitons	(	Eigen::MatrixXd &	FE_AB,
		Eigen::MatrixXd &	CTStates,
		BSE_OPERATOR	H,
		Eigen::MatrixXd &	J_dimer_out,
		Eigen::MatrixXd &	S_dimer_out,
		Diagnostics &	diag_out ) const

private

Compute J_pert and J_diag, and store raw J_dimer/S_dimer and diagnostics for later output.

Parameters

FE_AB	projected FE states in dimer basis
CTStates	CT states in dimer basis
H	BSE Hamiltonian operator
J_dimer_out	raw (pre-Lowdin) Hamiltonian matrix [out]
S_dimer_out	raw overlap matrix [out]
diag_out	diagnostics struct [out]

Returns: array of {J_pert, J_diag} matrices

Definition at line 794 of file bsecoupling.cc.

◆ ProjectFrenkelExcitons()

Eigen::MatrixXd votca::xtp::BSECoupling::ProjectFrenkelExcitons	(	const Eigen::MatrixXd &	BSE_Coeffs,
		const Eigen::MatrixXd &	X_AB,
		Index	bseX_vtotal,
		Index	bseX_ctotal,
		Index	bseAB_vtotal,
		Index	bseAB_ctotal ) const

private

Definition at line 325 of file bsecoupling.cc.

◆ SetupCTStates()

Eigen::MatrixXd votca::xtp::BSECoupling::SetupCTStates	(	Index	bseA_vtotal,
		Index	bseB_vtotal,
		Index	bseAB_vtotal,
		Index	bseAB_ctotal,
		const Eigen::MatrixXd &	A_AB,
		const Eigen::MatrixXd &	B_AB ) const

private

Definition at line 272 of file bsecoupling.cc.

◆ WriteMatrixToProperty()

void votca::xtp::BSECoupling::WriteMatrixToProperty	(	tools::Property &	prop,
		const std::string &	name,
		const Eigen::MatrixXd &	mat,
		double	conversion = 1.0 )

staticprivate

Write an Eigen matrix as rows of space-separated values into an XML property node. Each row becomes an attribute "row_N".

Parameters

prop	parent Property node to attach the matrix node to
name	name of the new child node
mat	matrix to write
conversion	optional unit conversion factor (default 1.0)

Definition at line 76 of file bsecoupling.cc.

◆ WriteToProperty()

void votca::xtp::BSECoupling::WriteToProperty	(	tools::Property &	summary,
		const QMState &	stateA,
		const QMState &	stateB ) const

private

Definition at line 98 of file bsecoupling.cc.

Member Data Documentation

◆ diag_singlet_

Diagnostics votca::xtp::BSECoupling::diag_singlet_

private

Definition at line 192 of file bsecoupling.h.

◆ diag_triplet_

Diagnostics votca::xtp::BSECoupling::diag_triplet_

private

Definition at line 193 of file bsecoupling.h.

◆ doSinglets_

bool votca::xtp::BSECoupling::doSinglets_

private

Definition at line 208 of file bsecoupling.h.

◆ doTriplets_

bool votca::xtp::BSECoupling::doTriplets_

private

Definition at line 207 of file bsecoupling.h.

◆ J_dimer_singlet_

Eigen::MatrixXd votca::xtp::BSECoupling::J_dimer_singlet_

private

Definition at line 186 of file bsecoupling.h.

◆ J_dimer_triplet_

Eigen::MatrixXd votca::xtp::BSECoupling::J_dimer_triplet_

private

Definition at line 188 of file bsecoupling.h.

◆ JAB_singlet

std::array<Eigen::MatrixXd, 2> votca::xtp::BSECoupling::JAB_singlet

private

Definition at line 180 of file bsecoupling.h.

◆ JAB_triplet

std::array<Eigen::MatrixXd, 2> votca::xtp::BSECoupling::JAB_triplet

private

Definition at line 181 of file bsecoupling.h.

◆ levA_

Index votca::xtp::BSECoupling::levA_

private

Definition at line 214 of file bsecoupling.h.

◆ levB_

Index votca::xtp::BSECoupling::levB_

private

Definition at line 215 of file bsecoupling.h.

◆ monomerA_energies_singlet_

Eigen::VectorXd votca::xtp::BSECoupling::monomerA_energies_singlet_

private

Definition at line 202 of file bsecoupling.h.

◆ monomerA_energies_triplet_

Eigen::VectorXd votca::xtp::BSECoupling::monomerA_energies_triplet_

private

Definition at line 204 of file bsecoupling.h.

◆ monomerB_energies_singlet_

Eigen::VectorXd votca::xtp::BSECoupling::monomerB_energies_singlet_

private

Definition at line 203 of file bsecoupling.h.

◆ monomerB_energies_triplet_

Eigen::VectorXd votca::xtp::BSECoupling::monomerB_energies_triplet_

private

Definition at line 205 of file bsecoupling.h.

◆ occA_

Index votca::xtp::BSECoupling::occA_

private

Definition at line 216 of file bsecoupling.h.

◆ occB_

Index votca::xtp::BSECoupling::occB_

private

Definition at line 218 of file bsecoupling.h.

◆ output_perturbation_

bool votca::xtp::BSECoupling::output_perturbation_

private

Definition at line 209 of file bsecoupling.h.

◆ output_tb_

bool votca::xtp::BSECoupling::output_tb_ = false

private

Definition at line 213 of file bsecoupling.h.

◆ S_dimer_singlet_

Eigen::MatrixXd votca::xtp::BSECoupling::S_dimer_singlet_

private

Definition at line 187 of file bsecoupling.h.

◆ S_dimer_triplet_

Eigen::MatrixXd votca::xtp::BSECoupling::S_dimer_triplet_

private

Definition at line 189 of file bsecoupling.h.

◆ unoccA_

Index votca::xtp::BSECoupling::unoccA_

private

Definition at line 217 of file bsecoupling.h.

◆ unoccB_

Index votca::xtp::BSECoupling::unoccB_

private

Definition at line 219 of file bsecoupling.h.

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

xtp/include/votca/xtp/bsecoupling.h
xtp/src/libxtp/bsecoupling.cc

Classes

Public Member Functions

Private Member Functions

Static Private Member Functions

Private Attributes

Additional Inherited Members

Detailed Description

Member Function Documentation

◆ Addoutput()

◆ CalcJ_dimer()

◆ CalculateCouplings()

◆ ComputeDiagnostics()

◆ Fulldiag()

◆ getSingletCouplingElement()

◆ getTripletCouplingElement()

◆ Identify()

◆ Initialize()

◆ OrthogonalizeCTs()

◆ Perturbation()

◆ ProjectExcitons()

◆ ProjectFrenkelExcitons()

◆ SetupCTStates()

◆ WriteMatrixToProperty()

◆ WriteToProperty()

Member Data Documentation

◆ diag_singlet_

◆ diag_triplet_

◆ doSinglets_

◆ doTriplets_

◆ J_dimer_singlet_

◆ J_dimer_triplet_

◆ JAB_singlet

◆ JAB_triplet

◆ levA_

◆ levB_

◆ monomerA_energies_singlet_

◆ monomerA_energies_triplet_

◆ monomerB_energies_singlet_

◆ monomerB_energies_triplet_

◆ occA_

◆ occB_

◆ output_perturbation_

◆ output_tb_

◆ S_dimer_singlet_

◆ S_dimer_triplet_

◆ unoccA_

◆ unoccB_