Valence Bond Perturbation Theory. A Valence Bond Method That Incorporates Perturbation Theory

Abstract

A post-VBSCF method, called valence bond second-order perturbation theory (VBPT2), is developed in this paper and is shown to be (i) economical and (ii) at par with more sophisticated VB and MO-based methods. The VBPT2 method starts with VBSCF using a minimal structure set. Subsequently, the Møller-Plesset (MP) partition of the zeroth-order Hamiltonian is obtained by introducing a generalized Fock matrix constructed from the VBSCF density matrix. The first-order wave function is expressed in terms of singly and doubly excited VB structures, which are generated by replacing occupied orbitals by virtual orbitals, the latter being defined as orthogonal to the occupied orbitals. The VBPT2 method retains the simplicity of a VB presentation by condensing contributions from the excited structures into the minimal number of fundamental structures that are involved in the VBSCF calculation. The method is tested by calculating the bond energies of H(2), F(2), N(2), O(2), the barrier of identity hydrogen abstraction reaction, the atomization energy and a potential energy curve for the water molecule and the structural weights and covalent-ionic resonance energy of F(2). It is shown that the VBPT2 method gives results in good agreement with those of the VBCI method and molecular-orbital based methods such as MRPT and MRCI at the same truncation levels. However, the computational effort is greatly reduced, compared to that of VBCI. Future potential directions for the development of the VBPT2 method are outlined.