Analytic projection from plane-wave and PAW wavefunctions and application to chemical-bonding analysis in solids

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, pl...

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Bibliographic Details
Published in:Journal of computational chemistry 2013-11, Vol.34 (29), p.2557-2567
Main Authors: Maintz, Stefan, Deringer, Volker L., Tchougréeff, Andrei L., Dronskowski, Richard
Format: Article
Language:English
Subjects:
chemical bonding
Chemical bonds
crystal orbital Hamilton population
density-functional theory
Eigenvalues
Mathematical functions
Nanoparticles
Numerical analysis
population analysis
projector augmented-wave method
Quantum physics
Solid state physics
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Summary: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 C60 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. An analytical framework is derived to transfer chemical information from periodic plane‐wave basis sets to local, Slater‐type orbitals. This way, projected densities of states and projected crystal orbital Hamilton population analyses are readily available for a range of state‐of‐the‐art materials simulations.
ISSN:0192-8651
1096-987X
DOI:10.1002/jcc.23424