Optimizing the Regularization in Size-Consistent Second-Order Brillouin-Wigner Perturbation Theory

TL;DR

This paper introduces an optimized regularization parameter for a size-consistent second-order Brillouin-Wigner perturbation theory, improving accuracy across various chemical datasets while maintaining computational efficiency.

Contribution

The work develops a semi-empirical optimization of the regularization parameter in BW-s2, enhancing its transferability and accuracy over traditional MP2 and energy-gap regularization methods.

Findings

Optimal alpha (4) improves accuracy across datasets.

BW-s2(alpha) depends on all amplitude information.

Method offers a promising route to higher-order correlation effects.

Abstract

Despite its simplicity and relatively low computational cost, second-order M{\o}ller-Plesset perturbation theory (MP2) is well-known to overbind noncovalent interactions between polarizable monomers and some organometallic bonds. In such situations, the pairwise-additive correlation energy expression in MP2 is inadequate. Although energy-gap dependent amplitude regularization can substantially improve the accuracy of conventional MP2 in these regimes, the same regularization parameter worsens the accuracy for small molecule thermochemistry and density-dependent properties. Recently, we proposed a repartitioning of Brillouin-Wigner perturbation theory that is size-consistent to second order (BW-s2), and a free parameter (${\alpha}$) was set to recover the exact dissociation limit of H2 in a minimal basis set. Alternatively ${\alpha}$ can be viewed as a regularization parameter, where each value of ${\alpha}$ represents a valid variant of BW-s2, which we denote as BW-s2(${\alpha}$). In this work, we semi-empirically optimize ${\alpha}$ for noncovalent interactions, thermochemistry, alkane conformational energies, electronic response properties, and transition metal datasets, leading to improvements in accuracy relative to the $\textit{ab initio}$ parameterization of BW-s2 and MP2. We demonstrate that the optimal ${\alpha}$ parameter (${\alpha} = 4$) is more transferable across chemical problems than energy-gap-dependent regularization parameters. This is attributable to the fact that the BW-s2(${\alpha}$) regularization strength depends on all of the information encoded in the t amplitudes rather than just orbital energy differences. While the computational scaling of BW-s2(${\alpha}$) is iterative $O(N^5)$, this effective and transferable approach to amplitude regularization is a promising route to incorporate higher-order correlation effects at second-order cost.