Benchmarking of the R-7 Anisotropic Dispersion Energy Term on the S22 Dimer Test Set.

The effects of including the anisotropic E7 term to the dispersion energy in addition to the leading E6 term are examined by using the effective fragment potential (EFP) method on the S22 test set. In this study, the full anisotropic E7 term is computed whereas the isotropic and spherical approximations are used for the E6 term. It is found that the E7 term is positive for hydrogen-bonded complexes and has a magnitude that can be as large as 50% of E6, giving rise to larger intermolecular distances than those obtained with E6 alone. The large positive value of E7 is analyzed for the hydrogen-bonded uracil dimer; it is found to originate from the large magnitude of the dynamic polarizability tensors as well as the proximity of the LMOs involved in hydrogen bonding. Conversely, E7 tends to be negative for dispersion-dominant complexes, and it has a very small magnitude for such complexes. The optimized geometries for these systems are therefore not greatly affected by the presence of the E7 term. For the mixed systems in the S22 test set, an intermediate behavior is observed. Overall, the E7 term is most important for systems with hydrogen bonding interactions and mixed systems. A full anisotropic treatment of the E6 term and higher order terms may need to be included to obtain more accurate interaction energies and geometries.