File LcaoMethod.h

Copyright

This code is licensed under the 3-clause BSD license.

Copyright ETH Zurich, Laboratory for Physical Chemistry, Reiher Group.

See LICENSE.txt for details.

namespace Scine

This header file contains functions that allow for common notation for common things that can be done at a different degree of derivatives.

This header contains alias definitions defining which classes to use for the different degrees of derivatives.

namespace Utils

class UnrestrictedCalculationNotAvailableException : public exception

Public Functions

const char *what() const

class LcaoMethod : public Scine::Utils::SinglePointMethod

#include <LcaoMethod.h>

Base class describing a method based on a LCAO ansatz.

Subclassed by Scine::Utils::ScfMethod

Getters and setters for matrices

const Eigen::MatrixXd &getOverlapMatrix() const

void setOverlapMatrix(const Eigen::MatrixXd &S)

const SpinAdaptedMatrix &getFockMatrix() const

void setFockMatrix(SpinAdaptedMatrix F)

const DensityMatrix &getDensityMatrix() const

void setDensityMatrix(DensityMatrix P)

MolecularOrbitals &getMolecularOrbitals()

const MolecularOrbitals &getMolecularOrbitals() const

void setMolecularOrbitals(MolecularOrbitals C)

const Eigen::MatrixXd &getEnergyWeightedDensityMatrix() const

void setEnergyWeightedDensityMatrix(const Eigen::MatrixXd &W)

Public Functions

LcaoMethod(bool unrestrictedCalculationPossible, Utils::derivOrder maximalOrder, bool orthogonalBasisSet = false)

virtual ~LcaoMethod()

virtual void initialize()

Initialize the method after the parameters have been set or loaded.

void calculate(Utils::derivativeType d)

Performs one single-point calculation of the energy.

Parameters

• derivativesOrder: which derivative to calculate up to, if possible.

void calculateDensityIndependentQuantities(Utils::derivativeType d = Utils::derivativeType::first)

void assembleFockMatrix()

void computeEnergyAndDerivatives(Utils::derivativeType d = Utils::derivativeType::first)

bool basisSetIsOrthogonal() const

Return

true if the basis set is orthogonal and the electronic structure is optimized in a normal eigenvalue problem, false if it is a generalized eigenvalue problem.

bool solvesOnlyOccupiedManifold() const

True if only the eigenpairs corresponding to the occupied MOs need to be calculated.

Subspace calculation is then performed with the Davidson-Liu Algorithm.

void setOnlyOccupiedManifoldToSolve(bool onlyOccupiedToSolve)

int getNumberElectrons() const

int getNumberAtomicOrbitals() const

void setMolecularCharge(int c)

int getMolecularCharge() const

void setSpinMultiplicity(int s)

int spinMultiplicity() const

void setUnrestrictedCalculation(bool b)

bool unrestrictedCalculationRunning() const

bool unrestrictedCalculationPossible() const

double getElectronicEnergy() const

double getRepulsionEnergy() const

double getHomoLumoGap() const

Get the HOMO-LUMO gap (Unit: Hartree).

const AtomsOrbitalsIndexes &getAtomsOrbitalsIndexesHolder() const

Returns a const reference to the object containing information about which atoms have how many orbitals and what their indexes are.

const SingleParticleEnergies &getSingleParticleEnergies() const

Returns a const reference to the object containing information about single-particle energies.

const LcaoUtils::ElectronicOccupation &getElectronicOccupation() const

Returns a const reference to the object containing information about the electronic occupation.

void setElectronicOccupationGenerator(std::unique_ptr<LcaoUtils::ElectronicOccupationGenerator> &&electronicOccupationSetter)

Set how the electronic occupation is to be set. By default, the Aufbau principle is used.

void addElectronicContribution(std::shared_ptr<AdditiveElectronicContribution> contribution)

Adds an electronic contribution to the Fock matrix.

void verifyPesValidity()

void calculateDensity()

Protected Functions

void resizeLcaoMethodMatrices()

Resets the size of the different matrices. To be called during initialization of the specific method.

void calculateOccupation()

void calculateEnergyWeightedDensity()

void calculateBondOrderMatrix()

void calculateAtomicCharges()

Protected Attributes

Eigen::MatrixXd overlapMatrix_

Eigen::MatrixXd energyWeightedDensityMatrix_

SpinAdaptedMatrix fockMatrix_

MolecularOrbitals eigenvectorMatrix_

DensityMatrix densityMatrix_

int nAOs_

int nElectrons_ = 0

int nElectronsForUnchargedSpecies_ = 0

SingleParticleEnergies singleParticleEnergies_

AtomsOrbitalsIndexes aoIndexes_

LcaoUtils::ElectronicOccupation occupation_

int molecularCharge_ = 0

bool unrestrictedCalculationPossible_

bool unrestrictedCalculationRunning_ = false

bool solveOnlyOccupiedManifold_ = false

int spinMultiplicity_ = 1

std::vector<double> coreCharges_

std::unique_ptr<LcaoUtils::ElectronicOccupationGenerator> electronicOccupationGenerator_

std::shared_ptr<StructureDependentInitializer> initializer_

std::shared_ptr<RepulsionCalculator> rep_

std::shared_ptr<OverlapCalculator> overlapCalculator_

std::shared_ptr<ElectronicContributionCalculator> electronicPart_

double electronicEnergy_

double repulsionEnergy_

Private Functions

void verifyChargeValidity()

void verifyMultiplicityValidity()

void verifyUnrestrictedValidity()

void calculateOccupationAndDensity()

template<Utils::derivativeType O>
void calculateDerivatives(Utils::AutomaticDifferentiation::DerivativeContainerType<O> &derivatives)

Private Members

const bool basisSetIsOrthogonal_