title: Predicting core level binding energies shifts: Suitability of the projector augmented wave approach as implemented in VASP.
abstract: Here, we assess the accuracy of various approaches implemented in Vienna ab initio simulation package code to estimate core-level binding energy shifts (ΔBEs) using a projector augmented wave method to treat core electrons. The performance of the Perdew-Burke-Ernzerhof (PBE) and the Tao-Perdew-Staroverov-Scuseria (TPSS) exchange-correlation density functionals is examined on a dataset of 68 molecules containing B→F atoms in diverse chemical environments, accounting for 185 different 1s core level binding energy shifts, for which both experimental gas-phase X-ray photoemission (XPS) data and accurate all electron ΔBEs are available. Four procedures to calculate core-level shifts are investigated. Janak-Slater transition state approach yields mean absolute errors of 0.37 (0.21) eV at PBE (TPSS) level, similar to highly accurate all electron ΔSCF approaches using same functionals, and close to XPS experimental accuracy of 0.1 eV. The study supports the use of these procedures to assign ΔBEs of molecular moieties on material surfaces of interest in surface science, nanotechnology, and heterogeneous catalysis. © 2017 Wiley Periodicals, Inc.
authors.affiliation: Departament de Ciència de Materials i Química Física & Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona, C/Martí i Franquès 1, Barcelona, 08028, Spain.
authors.forename: Noèlia
authors.initials: N
authors.lastname: Pueyo Bellafont
authors.affiliation: Departament de Ciència de Materials i Química Física & Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona, C/Martí i Franquès 1, Barcelona, 08028, Spain.
authors.forename: Francesc
authors.initials: F
authors.lastname: Viñes
authors.affiliation: Lehrstuhl für Theoretische Department Chemie und Pharmazie, Universität Erlangen-Nürnberg, Egerlandstraβe 3, Erlangen, 91058, Germany, Interdisciplinary Center for Molecular Materials (ICMM), Universität Erlangen-Nürnberg, Henkestraβe 42, Erlangen, 91054, Germany.
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Hieringer
authors.affiliation: Departament de Ciència de Materials i Química Física & Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona, C/Martí i Franquès 1, Barcelona, 08028, Spain.
authors.forename: Francesc
authors.initials: F
authors.lastname: Illas
keywords: X-ray photoemission; core level binding energy shifts; density functional theory; molecular dataset; projector augmented wave