An energy decomposition scheme applicable to strongly interacting systems

Abstract

An energy decomposition scheme useful for the analysis of the coupled types of interactions in strongly interacting systems is developed within the Hartree-Fock approximation. A dominant characteristic of the scheme is that it involves the interactions between vacant orbitals of component molecules, as can be justified from the third-order perturbation theory. On the basis ofab initio molecular orbital calculations, the utility of the scheme is illustrated for the BH₃-NH₃ complexation and the S_N2 reaction of CH₄ with H⁻. It is found that the charge transfer from electron donor (i.e. NH₃ or H⁻) to acceptor (i.e. BH₃ or CH₄) is strongly coupled with the polarization of the acceptor, to contribute appreciably to the stabilization of the entire system. A specific role of this coupling mode in the progress of reactions is discussed.