Band-Filling Correction Method for Accurate Adsorption Energy Calculations: A Cu/ZnO Case Study

Authors: Matti Hellström, Daniel Spångberg, Kersti Hermansson and Peter Broqvist

We present a simple method, the “band-filling correction”, to calculate accurateadsorption energies (Eads) in the low coverage limit from finite-size supercell slab calculations using DFT.

band-filling

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.

J. Chem. Theory Comput. 9, 4673 (2013).

DOI: 10.1021/ct400645v

Comments are closed.