A transferable quantum mechanical energy model for intermolecular interactions using a single empirical parameter

Abstract

The calculation of intermolecular interactions in molecular crystals using model energies provides a unified route to understanding the complex interplay of driving forces in crystallization, elastic properties and more. Presented here is a new single-parameter interaction energy model (CE-1p), extending the previous CrystalExplorer energy model and calibrated using density functional theory (DFT) calculations at the !B97M-V/def2-QZVP level over 1157 intermolecular interactions from 147 crystal structures. The new model incorporates an improved treatment of dispersion interactions and polarizabilities using the exchange-hole dipole model (XDM), along with the use of effective core potentials (ECPs), facilitating application to molecules containing elements across the periodic table (from H to Rn). This new model is validated against high-level reference data with outstanding performance, comparable to state-of-the-art DFT methods for molecular crystal lattice energies over the X23 set (mean absolute deviation 3.6 kJ mol–1) and for intermolecular interactions in the S66x8 benchmark set (root mean-square deviation 3.3 kJ mol–1). The performance of this model is further examined compared to the GFN2-xTB tight-binding model, providing recommendations for the evaluation of intermolecular interactions in molecular crystal systems.