Polyhalogenated Molecules in the Polarizable Ellipsoidal Force Field Model

TL;DR

This paper develops a polarizable ellipsoidal force field model to accurately simulate polyhalogenated molecules, capturing anisotropic electrostatic effects and demonstrating efficient parameter fitting for diverse compounds.

Contribution

It introduces a novel force field model that effectively accounts for halogen bond anisotropy and coupled {\sigma}-holes, with a practical, parallelizable parameter fitting protocol.

Findings

Accurately modeled anisotropic electrostatic potential in halogenated benzenes.

Reproduced symmetry of fitted parameters without additional constraints.

Efficient parameter fitting protocol suitable for large compound libraries.

Abstract

Polyhalogenated compounds are common in industrial, agricultural, and environmental applications. These compounds contain more halogen bonds than monohalogenated compounds. The presence of coupled {\sigma}-holes in the covalent halogen atoms, which demonstrates strong interplay in halogen bonds, should be carefully evaluated in force field optimization. In this study, a polarizable ellipsoidal force field model was successfully applied to many possible halogenated benzenes. The symmetry of the fitted parameters was reproduced without any additional restrictions. The optimized parameters for the anisotropic electrostatic potential showed good accuracy, stability, and transferability with reasonable physical meanings. The parameter fitting protocol was efficiently performed on a laptop, showing the potential of being completely parallelized for thousands of halogenated homologues.