A new energy decomposition scheme for molecular interactions within the Hartree‐Fock approximation

TLDR

Molecular interaction energies in the Hartree‑Fock framework are traditionally decomposed into exchange, polarization, and charge‑transfer components. The authors propose a new scheme to analyze the components of molecular interaction energy within the Hartree‑Fock approximation. They construct the supermolecule Fock matrix from isolated‑molecule.

Abstract

Abstract 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 .