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arXiv · 2109.05590

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

O. Jonathan Fajen·Kurt R. Brorsen
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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.

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O. Jonathan Fajen, Kurt R. Brorsen. 2021-11-28. Multicomponent MP4 and the Inclusion of Triple Excitations in Multicomponent Many-Body Methods. https://doi.org/10.1063/5.0071423

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