Analytic projection from plane-wave and PAW wavefunctions and application to chemical-bonding analysis in solids
Article first published online: 10 SEP 2013
Copyright © 2013 Wiley Periodicals, Inc.
Journal of Computational Chemistry
Volume 34, Issue 29, pages 2557–2567, 5 November 2013
How to Cite
How to cite this article: J. Comput. Chem. 2013, 34, 2557–2567. DOI: 10.1002/jcc.23424, , , .
- Issue published online: 24 SEP 2013
- Article first published online: 10 SEP 2013
- Manuscript Accepted: 7 AUG 2013
- Manuscript Revised: 30 JUL 2013
- Manuscript Received: 10 JUN 2013
- chemical bonding;
- crystal orbital Hamilton population;
- density-functional theory;
- population analysis;
- projector augmented-wave method
Quantum-chemical computations of solids benefit enormously from numerically efficient plane-wave (PW) basis sets, and together with the projector augmented-wave (PAW) method, the latter have risen to one of the predominant standards in computational solid-state sciences. Despite their advantages, plane waves lack local information, which makes the interpretation of local densities-of-states (DOS) difficult and precludes the direct use of atom-resolved chemical bonding indicators such as the crystal orbital overlap population (COOP) and the crystal orbital Hamilton population (COHP) techniques. Recently, a number of methods have been proposed to overcome this fundamental issue, built around the concept of basis-set projection onto a local auxiliary basis. In this work, we propose a novel computational technique toward this goal by transferring the PW/PAW wavefunctions to a properly chosen local basis using analytically derived expressions. In particular, we describe a general approach to project both PW and PAW eigenstates onto given custom orbitals, which we then exemplify at the hand of contracted multiple-ζ Slater-type orbitals. The validity of the method presented here is illustrated by applications to chemical textbook examples—diamond, gallium arsenide, the transition-metal titanium—as well as nanoscale allotropes of carbon: a nanotube and the fullerene. Remarkably, the analytical approach not only recovers the total and projected electronic DOS with a high degree of confidence, but it also yields a realistic chemical-bonding picture in the framework of the projected COHP method. © 2013 Wiley Periodicals, Inc.