Basis (linear algebra)

Computational chemistry

Chemistry

Materials science

Electronic engineering

Engineering

Geometry

Physics

Population

Electron

Charge density

Mathematics

Mulliken population analysis

Quantum mechanics

Demography

Computer science

Statistical physics

Density functional theory

Ionic bonding

Valence electron

Wave function

Sociology

Schematic

RSC Advances

Chemically understanding the electronic structure of a given material provides valuable information about its chemical as well as physical nature and, hence, is the key to designing materials with desired properties. For example, to rationalize the structures of solid-state materials in terms of the valence-electron distribution, highly schematic, essentially non-quantum-mechanical electron-partitioning models such as the Zintl-Klemm concept have been introduced by assuming idealized ionic charges. To go beyond the limits of the aforementioned concept, a Mulliken and Löwdin population analytical tool has been developed to accurately calculate the charges in solid-state materials solely from first-principles plane-wave-based computations. This population analysis tool, which has been implemented into the LOBSTER code, has been applied to diverse solid-state materials including polar intermetallics to prove its capability, including quick access to Madelung energies. In addition, a former weakness of the population analysis (namely, the basis-set dependency) no longer exists for the present approach which therefore represents a comparatively fast and accurate wave-function-based alternative for plane-wave calculations for which density-based charge approaches (e.g., Bader like) have been very popular.

Development of a robust tool to extract Mulliken and Löwdin charges from plane waves and its application to solid-state materials