New angles on standard force fields: towards a general approach for treating atomic-level anisotropy

TL;DR

This paper introduces MASTIFF, a new, efficient model that incorporates atomic-level anisotropy into force fields, improving accuracy in predicting intermolecular interactions for small organic molecules.

Contribution

The paper presents MASTIFF, a transferable and computationally-efficient model that includes atomic anisotropy effects in ab initio force fields, advancing beyond the sum-of-spheres approximation.

Findings

MASTIFF achieves high accuracy compared to high-level electronic structure theory.

It outperforms traditional sum-of-spheres models in benchmark tests.

The model is validated across a large library of intermolecular interactions.

Abstract

Nearly all standard force fields employ the 'sum-of-spheres' approximation, which models intermolecular interactions purely in terms of interatomic distances. Nonetheless, atoms in molecules can have significantly non-spherical shapes, leading to interatomic interaction energies with strong orientation dependencies. Neglecting this 'atomic-level anisotropy' can lead to significant errors in predicting interaction energies. Herein we propose a simple, transferable, and computationally-efficient model (MASTIFF) whereby atomic-level orientation dependence can be incorporated into ab initio intermolecular force fields. MASTIFF includes anisotropic exchange-repulsion, charge penetration, and dispersion effects, in conjunction with a standard treatment of anisotropic long-range (multipolar) electrostatics. To validate our approach, we benchmark MASTIFF against various sum-of-spheres models over a large library of intermolecular interactions between small organic molecules. MASTIFF achieves quantitative accuracy with respect to both high-level electronic structure theory and experiment, thus showing promise as a basis for 'next-generation' force field development.