title: Halogen bonds with benzene: an assessment of DFT functionals.
abstract: The performance of an extensive set of density functional theory functionals has been tested against CCSD(T) and MP2 results, extrapolated to the complete basis set (CBS) limit, for the interaction of either DCl or DBr (D = H, HCC, F, and NC) with the aromatic system of benzene. It was found that double hybrid functionals explicitly including dispersion, that is, B2PLYPD and mPW2PLYPD, provide the better agreement with the CCSD(T)/CBS results on both energies and equilibrium geometry, indicating the importance of dispersive contributions in determining this interaction. Among the less expensive functionals, the better performance is provided by the ωB97X and M062X functionals, while the ωB97XD and B97D functionals are shown to work very well for bromine complexes but not so well for chlorine complexes.
authors: Istituto di Scienze e Tecnologie Molecolari (ISTM), CNR, and INSTM UdR, Via Golgi 19, Milano, 20133, Italy.
authors: Alessandra
authors: A
authors: Forni
authors: Stefano
authors: S
authors: Pieraccini
authors: Stefano
authors: S
authors: Rendine
authors: Maurizio
authors: M
authors: Sironi
mesh_terms: D001554:Benzene / Q000737:chemistry*; D006219:Halogens / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D006219:Halogens; D001554:Benzene
keywords: benchmark calculations; density functional theory; halogen bond