Embedded-cluster calculations in a numeric atomic orbital density-functional theory framework

Daniel Berger; Andrew J Logsdail; Harald Oberhofer; Matthew R Farrow; C Richard A Catlow; Paul Sherwood; Alexey A Sokol; Volker Blum; Karsten Reuter

doi:10.1063/1.4885816

Embedded-cluster calculations in a numeric atomic orbital density-functional theory framework

J Chem Phys. 2014 Jul 14;141(2):024105. doi: 10.1063/1.4885816.

Authors

Daniel Berger¹, Andrew J Logsdail², Harald Oberhofer¹, Matthew R Farrow², C Richard A Catlow², Paul Sherwood³, Alexey A Sokol², Volker Blum⁴, Karsten Reuter¹

Affiliations

¹ Chair for Theoretical Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstr. 4, D-85747 Garching, Germany.
² Department of Chemistry, Kathleen Lonsdale Materials Chemistry, University College London, 20 Gordon St., London WC1H 0AJ, United Kingdom.
³ Scientific Computing Department, STFC Daresbury Laboratory, Daresbury, Warrington, United Kingdom.
⁴ Department of Mechanical Engineering and Materials Science, Duke University, Durham, North Carolina 27708, USA.

PMID: 25027997
DOI: 10.1063/1.4885816

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).