Accurate and Efficient ab Initio Calculations for Supramolecular Complexes: Symmetry-Adapted Perturbation Theory with Many-Body Dispersion.

Abstract

Symmetry-adapted perturbation theory (SAPT) provides a chemically meaningful energy decomposition scheme for nonbonded interactions that is useful for interpretive purposes. Although formally a dimer theory, we have previously introduced an "extended" version (XSAPT) that incorporates many-body polarization via self-consistent charge embedding. Here, we extend the XSAPT methodology to include nonadditive dispersion, using a modified form of the many-body dispersion (MBD) method of Tkatchenko and co-workers. Dispersion interactions beyond the pairwise atom-atom approximation improve total interaction energies even in small systems, and for large π-stacked complexes these corrections can amount to several kilocalories per mole. The XSAPT+MBD method introduced here achieves errors of ≲1 kcal/mol (as compared to high-level ab initio benchmarks) for the L7 data set of large dispersion-bound complexes and ≲4 kcal/mol (as compared to experiment) for the S30L data set of host-guest complexes. This is superior to the best contemporary density functional methods for noncovalent interactions, at comparable or lower cost. XSAPT+MBD represents a promising method for application to supramolecular assemblies, including protein-ligand binding.