title: Embedded-cluster calculations in a numeric atomic orbital density-functional theory framework.
abstract: We integrate the all-electron electronic structure code FHI-aims into the general ChemShell package for solid-state embedding quantum and molecular mechanical (QM/MM) calculations. A major undertaking in this integration is the implementation of pseudopotential functionality into FHI-aims to describe cations at the QM/MM boundary through effective core potentials and therewith prevent spurious overpolarization of the electronic density. Based on numeric atomic orbital basis sets, FHI-aims offers particularly efficient access to exact exchange and second order perturbation theory, rendering the established QM/MM setup an ideal tool for hybrid and double-hybrid level density functional theory calculations of solid systems. We illustrate this capability by calculating the reduction potential of Fe in the Fe-substituted ZSM-5 zeolitic framework and the reaction energy profile for (photo-)catalytic water oxidation at TiO2(110).
authors.affiliation: Chair for Theoretical Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstr. 4, D-85747 Garching, Germany.
authors.forename: Daniel
authors.initials: D
authors.lastname: Berger
authors.affiliation: Department of Chemistry, Kathleen Lonsdale Materials Chemistry, University College London, 20 Gordon St., London WC1H 0AJ, United Kingdom.
authors.forename: Andrew J
authors.initials: AJ
authors.lastname: Logsdail
authors.affiliation: Chair for Theoretical Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstr. 4, D-85747 Garching, Germany.
authors.forename: Harald
authors.initials: H
authors.lastname: Oberhofer
authors.affiliation: Department of Chemistry, Kathleen Lonsdale Materials Chemistry, University College London, 20 Gordon St., London WC1H 0AJ, United Kingdom.
authors.forename: Matthew R
authors.initials: MR
authors.lastname: Farrow
authors.affiliation: Department of Chemistry, Kathleen Lonsdale Materials Chemistry, University College London, 20 Gordon St., London WC1H 0AJ, United Kingdom.
authors.forename: C Richard A
authors.initials: CR
authors.lastname: Catlow
authors.affiliation: Scientific Computing Department, STFC Daresbury Laboratory, Daresbury, Warrington, United Kingdom.
authors.forename: Paul
authors.initials: P
authors.lastname: Sherwood
authors.affiliation: Department of Chemistry, Kathleen Lonsdale Materials Chemistry, University College London, 20 Gordon St., London WC1H 0AJ, United Kingdom.
authors.forename: Alexey A
authors.initials: AA
authors.lastname: Sokol
authors.affiliation: Department of Mechanical Engineering and Materials Science, Duke University, Durham, North Carolina 27708, USA.
authors.forename: Volker
authors.initials: V
authors.lastname: Blum
authors.affiliation: Chair for Theoretical Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstr. 4, D-85747 Garching, Germany.
authors.forename: Karsten
authors.initials: K
authors.lastname: Reuter