Benchmark assessment of the accuracy of several van der Waals density functionals

Abstract

The nonlocal correlation functional VV10, developed recently in our group, describes the whole range of dispersion interactions in a seamless and general fashion using only the electron density as input. The VV10 functional has a simple analytic form that can be adjusted for pairing with the exchange functional of choice. In this paper, we use several benchmark data sets of weakly interacting molecular complexes to test the accuracy of two VV10 variants, differing in their treatment of the exchange component. For the sake of comparison, several other density functionals suitable for noncovalent interactions were also tested against the same benchmarks. We find that the “default’’ version of VV10 with semilocal exchange gives very accurate geometries and binding energies for most van der Waals complexes but systematically overbinds hydrogen-bonded complexes. The alternative variant of VV10 with long-range corrected hybrid exchange performs exceptionally well for all types of weak bonding sampled in this study, including hydrogen bonds.