Many-Body Effects in Aqueous Systems: Synergies Between Interaction Analysis Techniques and Force Field Development

Annu Rev Phys Chem. 2023 Apr 24;74:337-360. doi: 10.1146/annurev-physchem-062422-023532.ABSTRACTInteraction analysis techniques, including the many-body expansion (MBE), symmetry-adapted perturbation theory, and energy decomposition analysis, allow for an intuitive understanding of complex molecular interactions. We review these methods by first providing a historical context for the study of many-body interactions and discussing how nonadditivities emerge from Hamiltonians containing strictly pairwise-additive interactions. We then elaborate on the synergy between these interaction analysis techniques and the development of advanced force fields aimed at accurately reproducing the Born-Oppenheimer potential energy surface. In particular, we focus on ab initio-based force fields that aim to explicitly reproduce many-body terms and are fitted to high-level electronic structure results. These force fields generally incorporate many-body effects through (a) parameterization of distributed multipoles, (b) explicit fitting of the MBE, (c) inclusion of many-atom features in a neural network, and (d) coarse-graining of many-body terms into an effective two-body term. We also discuss the emerging use of the MBE to improve the accuracy and speed of ab initio molecular dynamics.PMID:37093659 | DOI:10.1146/annurev-physchem-062422-023532
Source: Annual Review of Physical Chemistry - Category: Chemistry Authors: Source Type: research