Nonconventional partitioning of the many-body Hamiltonian for studying correlation effects

Abstract

For the treatment of electron correlation, one most often uses the Møller–Plesset (MP) partition which defines the zero-order Hamiltonian through the spectral resolution of the Fockian. We investigate how the MP partitioning can be improved while still using the Hartree–Fock (HF) reference state; and how the HF wave function can be substituted by a correlated one preserving the formal simplicity of the HF-based approach. To improve the MPn result, we introduce a fine tuning of energy denominators replacing the HF orbital energies with the ionization potentials obtained from the second-order Dyson equation. As this equation usually tends to close the gaps, a slight decrease of the denominators is expected, inducing an improvement of low-order correlation energies. We keep the simplicity of the MP partitioning and handle Dyson corrections as simple level shifts. Substituting doubly filled HF orbitals by strongly orthogonal geminals, one introduces a correlated reference state which is variational, size-consistent, and properly describes single-bond dissociation. This wave function, the antisymmetrized product of strongly orthogonal geminals (APSG), offers a good starting point for further corrections. We show that the use of an APSG reference state in the equation-of-motion technique leads to Tamm–Dankoff approach (TDA) equations which account for correlation effects in electronic excitation energies. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 70: 571–581, 1998