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


We examine the performance of a recently developed nonlocal density functional in predicting a model noncovalent interaction, namely 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 good general agreement with coupled-cluster calculations, though equilibrium distances are consistently overpredicted when using the revPBE functional for exchange. The new functional predicts changes in energy upon addition of halogen substituents correctly.

DOI: 10.1002/cphc.200700715

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@article{Hooper2008PredictingCI, title={Predicting C-H/pi interactions with nonlocal density functional theory.}, author={Joe Hooper and Valentino R. Cooper and Timo Thonhauser and Nichols A. Romero and Frank Zerilli and David C. Langreth}, journal={Chemphyschem : a European journal of chemical physics and physical chemistry}, year={2008}, volume={9 6}, pages={891-5} }