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

Abstract

Despite its simplicity and relatively low computational cost, second-order Møller-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 $\text{ab initio}$ 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.

7 pages main text, 7 pages supporting information, 11 figures

References in corpus (3)

• Localization and delocalization errors in density functional theory and implications for band-gap prediction
• Double-hybrid density-functional theory made rigorous
• Rigorous ab initio quantum embedding for quantum chemistry using Green's function theory: screened interaction, non-local self-energy relaxation, orbital basis, and chemical accuracy