Force Decomposition Analysis: A Method to Decompose Intermolecular Forces into Physically Relevant Component Contributions

Computational quantum chemistry can be more than just numerical experiments when methods are specifically adapted to investigate chemical concepts. One important example is the development of energy decomposition analysis (EDA) to reveal the physical driving forces behind intermolecular interactions. In EDA, typically the interaction energy from a good-quality density functional theory (DFT) calculation is decomposed into multiple additive components that unveil permanent and induced electrostatics, Pauli repulsion, dispersion, and charge-transfer contributions to noncovalent interactions. Herein, we formulate, implement, and investigate decomposing the forces associated with intermolecular interactions into the same components. The resulting force decomposition analysis (FDA) is potentially useful as a complement to the EDA to understand chemistry, while also providing far more information than an EDA for data analysis purposes such as training physics-based force fields. We apply the FDA based on absolutely localized molecular orbitals (ALMOs) to analyze interactions of water with sodium and chloride ions as well as in the water dimer. We also analyze the forces responsible for geometric changes in carbon dioxide upon adsorption onto (and activation by) gold and silver anions. We also investigate how the force components of an EDA-based force field for water clusters, namely MB-UCB, compare to those from force decomposition analysis.

Automated summary

Computational quantum chemistry becomes more than just numerical experiments when methods are tailored to explore chemical concepts. Energy decomposition analysis (EDA) is an important example, providing insights into the driving forces behind intermolecular interactions. The newly developed force decomposition analysis (FDA) complements EDA for understanding chemistry and offers more information for data analysis and force field training. By applying FDA, we analyze water interactions with sodium, chloride ions, and the water dimer, as well as the forces responsible for geometric changes of carbon dioxide adsorbed onto gold and silver anions.