Molecular Application of a State Specific Multi-Reference Brillouin-Wigner Perturbation Theory

Abstract

The single reference second order Brillouin-Wigner perturbation theory recently developed, which eliminates its size-extensivity error, has been generalized to state-specific, multi-reference (SS-MR), BWPT2 providing a size-extensive correction to the electron correlation problem for systems that demand the use of a multi-reference function. Illustrative numerical tests of the size-extensivity corrections are made for widely used molecules in their ground states, which are pronounced multi-reference characteristics. We have implemented two-reference and three-reference cases for CH2, BH and bond breaking process in the ground states of HF molecules. The results are compared with the rigorously size-extensive methods such as the Moller-Plesset perturbation theory, i.e., MP2, full configuration interaction (Full-CI) and allied methods using the same basis sets.