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 (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 DFT 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).

12 pages, 4 figures

References in corpus (4)

• Ab initio pseudopotentials for electronic structure calculations of poly-atomic systems using density-functional theory
• Resolution-of-identity approach to Hartree-Fock, hybrid density functionals, RPA, MP2, and \textit{GW} with numeric atom-centered orbital basis functions
• Random-phase approximation and its applications in computational chemistry and materials science
• First-principles thermodynamic screening approach to photo-catalytic water splitting with co-catalysts

Cited by in corpus (7)

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• Self-Consistent Green Function Embedding for Advanced Electronic Structure Methods Based on a Dynamical Mean-Field Concept
• Critical analysis of fragment-orbital DFT schemes for the calculation of electronic coupling values
• First-principles embedded-cluster calculations of the neutral and charged oxygen vacancy at the rutile TiO${}_2$(110) surface
• Theoretical evidence for unexpected O-rich phases at corners of MgO surfaces
• Quantum algorithms for scientific computing
• General embedded cluster protocol for accurate modeling of oxygen vacancies in metal-oxides