title: Accurate Treatment of Large Supramolecular Complexes by Double-Hybrid Density Functionals Coupled with Nonlocal van der Waals Corrections.
abstract: In this work, we present a thorough assessment of the performance of some representative double-hybrid density functionals (revPBE0-DH-NL and B2PLYP-NL) as well as their parent hybrid and GGA counterparts, in combination with the most modern version of the nonlocal (NL) van der Waals correction to describe very large weakly interacting molecular systems dominated by noncovalent interactions. Prior to the assessment, an accurate and homogeneous set of reference interaction energies was computed for the supramolecular complexes constituting the L7 and S12L data sets by using the novel, precise, and efficient DLPNO-CCSD(T) method at the complete basis set limit (CBS). The correction of the basis set superposition error and the inclusion of the deformation energies (for the S12L set) have been crucial for obtaining precise DLPNO-CCSD(T)/CBS interaction energies. Among the density functionals evaluated, the double-hybrid revPBE0-DH-NL and B2PLYP-NL with the three-body dispersion correction provide remarkably accurate association energies very close to the chemical accuracy. Overall, the NL van der Waals approach combined with proper density functionals can be seen as an accurate and affordable computational tool for the modeling of large weakly bonded supramolecular systems.
authors.affiliation: Instituto de Ciencia Molecular, Universidad de Valencia , E-46980 Valencia, Spain.
authors.forename: Joaquín
authors.initials: J
authors.lastname: Calbo
authors.affiliation: Instituto de Ciencia Molecular, Universidad de Valencia , E-46980 Valencia, Spain.
authors.forename: Enrique
authors.initials: E
authors.lastname: Ortí
authors.affiliation: Departamento de Química Física, Universidad de Alicante , E-03080 Alicante, Spain.
authors.forename: Juan C
authors.initials: JC
authors.lastname: Sancho-García
authors.affiliation: Instituto de Ciencia Molecular, Universidad de Valencia , E-46980 Valencia, Spain.
authors.forename: Juan
authors.initials: J
authors.lastname: Aragó
mesh_terms: D003198:Computer Simulation; D057927:Hydrophobic and Hydrophilic Interactions; D046911:Macromolecular Substances / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D011789:Quantum Theory
chemical_list: D046911:Macromolecular Substances