title: Using Nonempirical Semilocal Density Functionals and Empirical Dispersion Corrections to Model Dative Bonding in Substituted Boranes.
abstract: Dative bonds to substituted boranes represent a challenge for the approximate exchange-correlation functionals typically used in density functional theory (DFT). Accurately modeling these bonds with DFT has usually required highly parametrized functionals, large admixtures of exact exchange, or computationally expensive double hybrids. This work shows that the nonempirical semilocal PBEsol functional, and the nonempirical semilocal PBE and TPSS functionals augmented with empirical interatomic dispersion corrections, accurately treat several representative problems in dative bonding. These methods typically surpass the MPW1K "kinetics" global hybrid previously recommended for dative bonds. This work also provides additional insights into the accuracy of the parametrized M06 functionals and indicates some deficiencies of the B97-D functional relative to PBE-D and TPSS-D. Applications to frustrated Lewis pairs illustrate the potential of these methods.
authors.affiliation: Department of Chemistry, Texas Christian University Fort Worth, Texas 76109.
authors.forename: Benjamin G
authors.initials: BG
authors.lastname: Janesko