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

Journal Article (Journal Article)

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).

Full Text

Duke Authors

Cited Authors

  • Berger, D; Logsdail, AJ; Oberhofer, H; Farrow, MR; Catlow, CRA; Sherwood, P; Sokol, AA; Blum, V; Reuter, K

Published Date

  • July 2014

Published In

Volume / Issue

  • 141 / 2

Start / End Page

  • 024105 -

PubMed ID

  • 25027997

Electronic International Standard Serial Number (EISSN)

  • 1089-7690

International Standard Serial Number (ISSN)

  • 0021-9606

Digital Object Identifier (DOI)

  • 10.1063/1.4885816


  • eng