title: Dispersion Interactions with Density-Functional Theory: Benchmarking Semiempirical and Interatomic Pairwise Corrected Density Functionals.
abstract: We present a comparative assessment of the accuracy of two different approaches for evaluating dispersion interactions: interatomic pairwise corrections and semiempirical meta-generalized-gradient-approximation (meta-GGA)-based functionals. This is achieved by employing conventional (semi)local and (screened-)hybrid functionals, as well as semiempirical hybrid and nonhybrid meta-GGA functionals of the M06 family, with and without interatomic pairwise Tkatchenko-Scheffler corrections. All of those are tested against the benchmark S22 set of weakly bound systems, a representative larger molecular complex (dimer of NiPc molecules), and a representative dispersively bound solid (hexagonal boron nitride). For the S22 database, we also compare our results with those obtained from the pairwise correction of Grimme (DFT-D3) and nonlocal Langreth-Lundqvist functionals (vdW-DF1 and vdW-DF2). We find that the semiempirical kinetic-energy-density dependence introduced in the M06 functionals mimics some of the nonlocal correlation needed to describe dispersion. However, long-range contributions are still missing. Pair-wise interatomic corrections, applied to conventional semilocal or hybrid functionals, or to M06 functionals, provide for a satisfactory level of accuracy irrespectively of the underlying functional. Specifically, screened-hybrid functionals such as the Heyd-Scuseria-Ernzerhof (HSE) approach reduce self-interaction errors in systems possessing both localized and delocalized orbitals and can be applied to both finite and extended systems. Therefore, they serve as a useful underlying functional for dispersion corrections.
authors.affiliation: Department of Materials and Interfaces, Weizmann Institute of Science , Rehovoth 76100, Israel.|Center for Computational Materials, Institute for Computational Engineering and Sciences, University of Texas at Austin , Austin, Texas 78712, United States.
authors.forename: Noa
authors.initials: N
authors.lastname: Marom
authors.affiliation: Fritz-Haber-Institut der Max-Planck-Gesellschaft , Faradayweg 4-6, 14195 Berlin, Germany.
authors.forename: Alexandre
authors.initials: A
authors.lastname: Tkatchenko
authors.affiliation: Fritz-Haber-Institut der Max-Planck-Gesellschaft , Faradayweg 4-6, 14195 Berlin, Germany.
authors.forename: Mariana
authors.initials: M
authors.lastname: Rossi
authors.affiliation: Fritz-Haber-Institut der Max-Planck-Gesellschaft , Faradayweg 4-6, 14195 Berlin, Germany.
authors.forename: Vivekanand V
authors.initials: VV
authors.lastname: Gobre
authors.affiliation: School of Chemistry, The Sackler Faculty of Exact Sciences, Tel Aviv University , Tel Aviv 69978, Israel.
authors.forename: Oded
authors.initials: O
authors.lastname: Hod
authors.affiliation: Fritz-Haber-Institut der Max-Planck-Gesellschaft , Faradayweg 4-6, 14195 Berlin, Germany.
authors.forename: Matthias
authors.initials: M
authors.lastname: Scheffler
authors.affiliation: Department of Materials and Interfaces, Weizmann Institute of Science , Rehovoth 76100, Israel.
authors.forename: Leeor
authors.initials: L
authors.lastname: Kronik