Evaluating London Dispersion Interactions in DFT: A Nonlocal Anisotropic Buckingham–Hirshfeld Model

In this work, we present a novel model, referred to as BH-DFT-D, for the evaluation of London dispersion, with the purpose to correct the performance of local DFT exchange-correlation functionals for the description of van der Waals interactions. The new BH-DFT-D model combines the equations originally derived by Buckingham [Buckingham, A. D. Adv. Chem. Phys1967, 12, 107] with the definition of distributed multipole polarizability tensors within the Hirshfeld method [Hirshfeld, F.L. Theor. Chim. Acta1977, 44, 129], resulting in nonlocal, fully anisotropic expressions. Since no damping function has been introduced yet into the model, it is suitable in its present form for the evaluation of dispersion interactions in van der Waals dimers with no or negligible overlap. The new method is tested for an extended collection of van der Waals dimers against high-level data, where it is found to reproduce interaction energies at the BH-B3LYP-D/aug-cc-pVTZ level with a mean average error (MAE) of 0.20 kcal/mol. Next, development steps of the model will consist of adding a damping function, analytical gradients, and generalization to a supramolecular system.