A Simple Electron-Density Based Force Field Model for High-Energy Interactions between Atoms and Molecules

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2024-02, Vol.128 (6), p.1163-1172
• Main Authors: Romero, José, Limão-Vieira, Paulo, Hermansson, Kersti, Probst, Michael
• Format: Article
• Language: English
• Subjects: A: New Tools and Methods in Experiment and Theory
• ISSN: 1089-5639; 1520-5215; 1520-5215
• DOI: 10.1021/acs.jpca.3c06724

In high-energy molecular dynamics or Monte Carlo simulations, standard force fields optimized for simulations at ambient temperatures are inadequate. This is largely because their repulsive parts have been regarded as not very significant, even well below zero interaction energies. It is, therefore, not obvious which force fields to resort to for simulating hot gases or plasmas. A force field model that uses the electronic densities of noninteracting atoms or molecules within the pair approximation is introduced. We start by deriving a naïve model that neglects any exchange and correlation effects between the electronic clouds and then correct this model by adding a term calibrated from ab initio calculations using the CCSD­(T)/cc-pVTZ level of theory. The resulting expression for this term can be regarded as a simple exchange–correlation function. We compare the results for the repulsive part of the potential energy hypersurfaces with the force fields commonly used on some dimers of small molecules.