Development of a Non-Empirical Exchange-Hole Dipole Moment Dispersion Model

Abstract

The inclusion of dispersion effects is important in density-functional theory (DFT) to model non-covalent interactions correctly, a task that is essential in many applications of the theory. Many dispersion functionals have been proposed in the past. The exchange-hole dipole moment (XDM) model combines the simplicity of a damped pairwise asymptotic expression for the dispersion energy with a theory-grounded approach to calculate the dispersion coefficients. XDM is, arguably, the most accurate dispersion correction for the description of molecular crystals and it has been thoroughly tested for other applications across a wide range of chemistries. Here, we address the two main shortcomings of XDM. First, XDM relies on the use of experimentally determined free-atom polarizabilities. Second, because the XDM atom-in-molecule properties (volumes, polarizabilities, exchange-hole dipole moments) use the Hirshfeld partition method, XDM describes systems with large atomic partial charges, like alkali cations or halide anions, poorly. We propose neXDM, a non-empirical variant of XDM that removes the experimental parameters by using the Kirkwood polarizability formula, thereby making neXDM a pure meta-GGA dispersion functional. In addition, following previous work by Bu\v{c}ko et al. on the similar Tkatchenko--Scheffler (TS) method, we replace the Hirshfeld partitioning with its iterative counterpart. The performance of neXDM is shown to be on par with XDM in standard molecular and crystal benchmark sets, and greatly improves the modeling of ionic systems. The new neXDM method sets a new record for the best dispersion-corrected generalized-gradient approximation (GGA) functional for molecular crystal lattice energies in the X23 set (0.700~kcal/mol).