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A new energy decomposition scheme for molecular interactions within the Hartree‐Fock approximation
Author(s) -
Kitaura Kazuo,
Morokuma Keiji
Publication year - 1976
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560100211
Subject(s) - supermolecule , fock matrix , hartree–fock method , basis set , molecular orbital , atomic orbital , chemistry , quantum mechanics , matrix (chemical analysis) , computational chemistry , physics , electron , molecule , density functional theory , chromatography
A new method is proposed for the analysis of components of molecular interaction energy within the Hartree‐Fock approximation. The Hartree‐Fock molecular orbitals of the isolated molecules are used as the basis for the construction of Fock matrix of the supermolecule. Then certain blocks of this matrix are set to zero subject to specify boundary conditions of the supermolecule molecular orbitals, and the resultant matrix is diagonalized iteratively to obtain the desired energy components. This method can be considered as an extension of our previous method, but has an advantage in the explicit definition of the charge transfer energy, placing it on an equal footing with the exchange and polarization terms. The new method is compared with existing perturbation methods, and is also applied to the energy and electron density decomposition of (H 2 O) 2 .