An efficient algorithm for the density-functional theory treatment of dispersion interactions

Abstract

The quasi-self-consistent-field dispersion-corrected density-functional theory formalism (QSCF-DC-DFT) is developed and presented as an efficient and reliable scheme for the DFT treatment of van der Waals dispersion complexes, including full geometry optimizations and frequency calculations with analytical energy derivatives in a routine way. For this purpose, the long-range-corrected Perdew-Burke-Ernzerhof exchange functional and the one-parameter progressive correlation functional of Hirao and co-workers are combined with the Andersson-Langreth-Lundqvist (ALL) long-range correlation functional. The time-consuming self-consistent incorporation of the ALL term in the DFT iterations needed for the calculation of forces and force constants is avoided by an a posteriori evaluation of the ALL term and its gradient based on an effective partitioning of the coordinate space into global and intramonomer coordinates. QSCF-DC-DFT is substantially faster than SCF-DC-DFT would be. QSCF-DC-DFT is used to explore the potential energy surface (PES) of the benzene dimer. The results for the binding energies and intermolecular distances agree well with coupled-cluster calculations at the complete basis-set limit. We identify 16 stationary points on the PES, which underlines the usefulness of analytical energy gradients for the investigation of the PES. Furthermore, the inclusion of analytically calculated zero point energies reveals that large-amplitude vibrations connect the eight most stable benzene dimer forms and make it difficult to identify a dominating complex form. The tilted T structure and the parallel-displaced sandwich form have the same D(0) value of 2.40 kcal/mol, which agrees perfectly with the experimental value of 2.40+/-0.40 kcal/mol.