title: Band-Filling Correction Method for Accurate Adsorption Energy Calculations: A Cu/ZnO Case Study.
abstract: We present a simple method, the "band-filling correction", to calculate accurate adsorption energies (Eads) in the low coverage limit from finite-size supercell slab calculations using DFT. We show that it is necessary to use such a correction if charge transfer takes place between the adsorbate and the substrate, resulting in the substrate bands either filling up or becoming depleted. With this correction scheme, we calculate Eads of an isolated Cu atom adsorbed on the ZnO(101̅0) surface. Without the correction, the calculated Eads is highly coverage-dependent, even for surface supercells that would typically be considered very large (in the range from 1 nm × 1 nm to 2.5 nm × 2.5 nm). The correction scheme works very well for semilocal functionals, where the corrected Eads is converged within 0.01 eV for all coverages. The correction scheme also works well for hybrid functionals if a large supercell is used and the exact exchange interaction is screened.
authors.affiliation: Department of Chemistry, The Ångström Laboratory, Uppsala University , P.O. Box 538, SE-751 21 Uppsala, Sweden.
authors.forename: Matti
authors.initials: M
authors.lastname: Hellström
authors.affiliation: Department of Chemistry, The Ångström Laboratory, Uppsala University , P.O. Box 538, SE-751 21 Uppsala, Sweden.
authors.forename: Daniel
authors.initials: D
authors.lastname: Spångberg
authors.affiliation: Department of Chemistry, The Ångström Laboratory, Uppsala University , P.O. Box 538, SE-751 21 Uppsala, Sweden.
authors.forename: Kersti
authors.initials: K
authors.lastname: Hermansson
authors.affiliation: Department of Chemistry, The Ångström Laboratory, Uppsala University , P.O. Box 538, SE-751 21 Uppsala, Sweden.
authors.forename: Peter
authors.initials: P
authors.lastname: Broqvist