Self-consistent charge embedding at very low cost, with application to symmetry-adapted perturbation theory

Abstract

Extended symmetry-adapted perturbation theory (XSAPT) uses a self-consistent charge embedding to capture many-body polarization, in conjunction with a pairwise-additive SAPT calculation of intermolecular interaction energies. The original implementation of XSAPT is based on charges that are fit to reproduce molecular electrostatic potentials, but this becomes a computational bottleneck in large systems. Charge embedding based on modified Hirshfeld atomic charges is reported here, which dramatically reduces the computational cost without compromising accuracy. Exemplary calculations are presented for supramolecular complexes such as C₆₀@C₆₀H₂₈, a DNA intercalation complex, and a 323-atom model of a drug molecule bound to an enzyme active site. The proposed charge embedding should be useful in other fragment-based quantum chemistry methods as well.