Correction to DFT Interaction Energies by an Empirical Dispersion Term Valid for a Range of Intermolecular Distances

The computation of intermolecular interaction energies via commonly used density functionals is hindered by their inaccurate inclusion of medium and long range dispersion interactions. Computation of inter- and intra-molecule interaction energies as well as computational design of (bio)materials, requires a fairly accurate yet not overly expensive methodology. It is also desirable to compute intermolecular energies not only at their equilibrium (lowest energy) configurations but also over a range of distances. We present a method to compute intermolecular interaction energies by including an empirical correction for dispersion which is valid over a range of intermolecular distances. This is achieved by optimizing parameters that moderate the empirical correction by explicit comparison of density functional (GGA) energies with distance-dependent (DD) reference values obtained at the CCSD(T)/CBS limit. The resulting GGA-DD method yields interaction energies with an accuracy generally better than 1 kcal/mol for different types of noncovalent complexes, over a range of intermolecular distances and interaction strengths, relative to the expensive CCSD(T)/CBS standard