Fragment Orbitals Extracted from First-Principles Plane-Wave Calculations

Inorganic Chemistry, vol. 63, pp. 20161–20172

Abstract

Decomposing extended structures into smaller, molecular, even functional groups or simple fragments has a long tradition in chemistry because it allows for understanding certain electronic peculiarities in truly chemical terms. By doing so, invaluable property information is chemically accessible, for example, needed to rationalize catalytic or magnetic or optical nature. In order to also follow that train of thought for periodic materials, we have developed a tool which in a straightforward manner derives fragment molecular orbitals from plane-wave electronic-structure data of whatever kind of solid-state material. We here report on the mathematical apparatus of the method dubbed linear combination of fragment orbitals (LCFO) used for that purpose, implemented within the LOBSTER code. The method is illustrated from various sorts of molecular entities contained in such crystalline materials, together with an assessment of both accuracy and robustness of the new tool.

Authors 5

1. Peter C. Müller Aachen Chair of Solid-State and Quantum Chemistry Institute of Inorganic Chemistry

   Institute of Inorganic Chemistry of the Slovak Academy of Sciences · RWTH Aachen University

   Affiliation as printed

   Chair of Solid-State and Quantum Chemistry, Institute of Inorganic Chemistry

   RWTH Aachen University

   Chair of Solid-State and Quantum Chemistry, Institute of Inorganic Chemistry, RWTH Aachen University, 52056 Aachen, Germany

2. Nathalie Schmit Aachen Chair of Solid-State and Quantum Chemistry Institute of Inorganic Chemistry

   Institute of Inorganic Chemistry of the Slovak Academy of Sciences · RWTH Aachen University

   Affiliation as printed

   Chair of Solid-State and Quantum Chemistry, Institute of Inorganic Chemistry

   RWTH Aachen University

   Chair of Solid-State and Quantum Chemistry, Institute of Inorganic Chemistry, RWTH Aachen University, 52056 Aachen, Germany

3. Leander Sann Aachen Chair of Solid-State and Quantum Chemistry Institute of Inorganic Chemistry

   Institute of Inorganic Chemistry of the Slovak Academy of Sciences · RWTH Aachen University

   Affiliation as printed

   Chair of Solid-State and Quantum Chemistry, Institute of Inorganic Chemistry

   RWTH Aachen University

   Chair of Solid-State and Quantum Chemistry, Institute of Inorganic Chemistry, RWTH Aachen University, 52056 Aachen, Germany

4. Simon Steinberg Aachen Chair of Solid-State and Quantum Chemistry Institute of Inorganic Chemistry

   Institute of Inorganic Chemistry of the Slovak Academy of Sciences · RWTH Aachen University

   Affiliation as printed

   Chair of Solid-State and Quantum Chemistry, Institute of Inorganic Chemistry

   RWTH Aachen University

   Chair of Solid-State and Quantum Chemistry, Institute of Inorganic Chemistry, RWTH Aachen University, 52056 Aachen, Germany

5. Richard Dronskowski corresponding Aachen Chair of Solid-State and Quantum Chemistry Institute of Inorganic Chemistry

   Institute of Inorganic Chemistry of the Slovak Academy of Sciences · RWTH Aachen University

   Affiliation as printed

   Chair of Solid-State and Quantum Chemistry, Institute of Inorganic Chemistry

   RWTH Aachen University

   Chair of Solid-State and Quantum Chemistry, Institute of Inorganic Chemistry, RWTH Aachen University, 52056 Aachen, Germany