Domain-averaged Fermi-hole Analysis for Solids

0389634 - ÚCHP 2013 RIV US eng J - Journal Article
Baranov, A. - Ponec, Robert - Kohout, M.
Domain-averaged Fermi-hole Analysis for Solids.
Journal of Chemical Physics. Roč. 137, č. 21 (2012), s. 214109. ISSN 0021-9606. E-ISSN 1089-7690
R&D Projects: GA ČR GA203/09/0118
Institutional support: RVO:67985858
Keywords : bonding in solids * domain averaged fermi hole * natural orbitals
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 3.164, year: 2012

The domain-averaged Fermi hole (DAFH) orbitals provide highly visual representation of bonding in terms of orbital-like functions with attributed occupation numbers. It was successfully applied on many molecular systems including those with non-trivial bonding patterns. This article reports for the first time the extension of the DAFH analysis to the realm of extended periodic systems. Simple analytical model of DAFH orbital for single-band solids is introduced which allows to rationalize typical features that DAFH orbitals for extended systems may possess. In particular, a connection between Wannier and DAFH orbitals has been analyzed. The analysis of DAFH orbitals on the basis of DFT calculations is applied to hydrogen lattices of different dimensions as well as to the solids diamond, graphite, Na, Cu and NaCl. In case of hydrogen lattices, remarkable similarity is found between the DAFH orbitals evaluated with both the analytical approach and DFT. In case of the selected ionic and covalent solids the DAFH orbitals deliver bonding descriptions, which are compatible with classical orbital interpretation. For metals the DAFH analysis shows essential multicenter nature of bonding.
Permanent Link: http://hdl.handle.net/11104/0218533