Repartitioned Brillouin-Wigner Perturbation Theory with a Size-Consistent Second-Order Correlation Energy

TL;DR

This paper introduces a size-consistent second-order Brillouin-Wigner perturbation theory (BW-s2) that improves upon MP2 and rivals CCSD in accuracy for various chemical systems, addressing divergence issues in small-gap molecules.

Contribution

It proposes a novel Hamiltonian partitioning leading to a regular, size-extensive, and orbital invariant BWPT method applicable to diverse chemical problems.

Findings

BW-s2 correctly describes H2 dissociation in minimal basis

BW-s2 outperforms MP2 in bond breaking and noncovalent interactions

BW-s2 rivals CCSD for thermochemical accuracy

Abstract

Second-order M{\o}ller-Plesset perturbation theory (MP2) often breaks down catastrophically in small-gap systems, leaving much to be desired in its performance for myriad chemical applications such as noncovalent interactions, thermochemistry, and dative bonding in transition metal complexes. This divergence problem has reignited interest in Brillouin-Wigner perturbation theory (BWPT), which is regular at all orders but lacks size-consistency and extensivity, severely limiting its application to chemistry. In this work, we propose an alternative partitioning of the Hamiltonian that leads to a regular BWPT perturbation series that, through second order, is size-extensive, size-consistent (provided its Hartree-Fock reference is also), and orbital invariant. Our second-order size-consistent Brillouin-Wigner (BW-s2) approach is capable of describing the exact dissociation limit of H$_2$ in a minimal basis set regardless of the spin-polarization of the reference orbitals. More broadly, we find that BW-s2 offers improvements relative to MP2 for covalent bond breaking, noncovalent interaction energies, and metal/organic reaction energies, while rivaling coupled-cluster with single and double substitutions (CCSD) for thermochemical properties.