GGA-Level Subsystem DFT Achieves Sub-kcal/mol Accuracy Intermolecular Interactions by Mimicking Nonlocal Functionals.

Abstract

The key feature of nonlocal kinetic energy functionals is their ability to reduce to the Thomas-Fermi functional in the regions of high density and to the von Weizsäcker functional in the region of low-density/high reduced density gradient. This behavior is crucial when these functionals are employed in subsystem DFT simulations to approximate the nonadditive kinetic energy. We propose a GGA nonadditive kinetic energy functional which mimics the good behavior of nonlocal functionals, retaining the computational complexity of typical semilocal functionals. Crucially, this functional depends on the inter-subsystem density overlap. The new functional reproduces Kohn-Sham DFT and benchmark CCSD(T) interaction energies of weakly interacting dimers in the S22-5 and S66 test sets with a mean absolute deviation well below 1 kcal/mol.