Optimized damping parameters for empirical dispersion corrections to symmetry-adapted perturbation theory

Abstract

Symmetry-adapted perturbation theory (SAPT) has become an invaluable tool for studying the fundamental nature of non-covalent interactions by directly computing the electrostatics, exchange (steric) repulsion, induction (polarization), and London dispersion contributions to the interaction energy using quantum mechanics. Further application of SAPT is primarily limited by its computational expense, where even its most affordable variant (SAPT0) scales as the fifth power of system size [O(N⁵)] due to the dispersion terms. The algorithmic scaling of SAPT0 is reduced from O(N⁵)→O(N⁴) by replacing these terms with the empirical D3 dispersion correction of Grimme and co-workers, forming a method that may be termed SAPT0-D3. Here, we optimize the damping parameters for the -D3 terms in SAPT0-D3 using a much larger training set than has previously been considered, namely, 8299 interaction energies computed at the complete-basis-set limit of coupled cluster through perturbative triples [CCSD(T)/CBS]. Perhaps surprisingly, with only three fitted parameters, SAPT0-D3 improves on the accuracy of SAPT0, reducing mean absolute errors from 0.61 to 0.49 kcal mol^-1 over the full set of complexes. Additionally, SAPT0-D3 exhibits a nearly 2.5× speedup over conventional SAPT0 for systems with ∼300 atoms and is applied here to systems with up to 459 atoms. Finally, we have also implemented a functional group partitioning of the approach (F-SAPT0-D3) and applied it to determine important contacts in the binding of salbutamol to G-protein coupled β₁-adrenergic receptor in both active and inactive forms. SAPT0-D3 capabilities have been added to the open-source Psi4 software.