Predicting C-H/$\pi$ interactions with nonlocal density functional theory

Abstract

We examine the performance of a recently developed nonlocal density functional in predicting a model noncovalent interaction, the weak bond between an aromatic $\pi$ system and an aliphatic C-H group. The new functional is a significant improvement over traditional density functionals, providing results which compare favorably to high-level quantum-chemistry techniques but at considerably lower computational cost. Interaction energies in several model C-H/$\pi$ systems are in generally good agreement with coupled-cluster calculations, though equilibrium distances are consistently overpredicted when using the revPBE functional for exchange. The new functional correctly predicts changes in energy upon addition of halogen substituents.