Multicomponent MP4 and the Inclusion of Triple Excitations in Multicomponent Many-Body Methods

TL;DR

This paper introduces full multicomponent MP3 and MP4 methods, including connected triples, and compares their accuracy to existing coupled-cluster methods, revealing insights into their relative performance and the significance of triple excitations.

Contribution

First implementation of full multicomponent MP3 and MP4 methods including connected triples, providing new insights into their accuracy and the role of triple excitations in electron-proton correlation.

Findings

Multicomponent MP3 is comparable to coupled-cluster doubles for proton affinities.

Multicomponent MP4 has similar accuracy to CCSD.

Electron-electron triple contributions can be ignored with minimal accuracy loss.

Abstract

This study implements the full multicomponent third-order (MP3) and fourth-order (MP4) many-body perturbation theory methods for the first time. Previous multicomponent studies have only implemented a subset of the full contributions and the present implementation is the first multicomponent many-body method to include any connected triples contribution to the electron-proton correlation energy. The multicomponent MP3 method is shown to be comparable in accuracy to the multicomponent coupled-cluster doubles method for the calculation of proton affinities, while the multicomponent MP4 method is of similar accuracy as the multicomponent coupled-cluster singles and doubles (CCSD) method. From the results in this study, it is hypothesized that the relative accuracy of multicomponent methods is more similar to their single-component counterparts than previously assumed and that the previous explanation for the better performance of multicomponent CCSD compared to other ab initio multicomponent methods may be incorrect. It is demonstrated that for multicomponent MP4, the fourth-order triple-excitation contributions can be split into electron-electron and electron-proton contributions and the electron-electron contributions ignored with very little loss of accuracy of protonic properties.