Accurate Noncovalent Interactions via Dispersion-Corrected Second-Order Møller–Plesset Perturbation Theory

Noncovalent interactions govern many important areas of chemistry, ranging from biomolecules to molecular crystals. Here, an accurate and computationally inexpensive dispersion-corrected second-order Møller–Plesset perturbation theory model (MP2D) is presented. MP2D recasts the highly successful dispersion-corrected MP2C model in a framework based on Grimme’s D3 dispersion correction, combining Grimme’s D3 dispersion coefficients with new analogous uncoupled Hartree–Fock ones and five global empirical parameters. MP2D is faster than MP2C, and unlike MP2C, it is suitable for geometry optimizations and can describe both intra- and intermolecular noncovalent interactions with high accuracy. MP2D approaches the accuracy of higher-level ab initio wave function techniques and out-performs a widely used hybrid dispersion-corrected density functional on a range of intermolecular, intramolecular, and thermochemical benchmarks.