Extending Hirshfeld-I to bulk and periodic materials

Authors

  • Danny E. P. Vanpoucke,

    Corresponding author
    1. SCRiPTS Group, Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281-S3, Gent 9000, Belgium
    2. Ghent Quantum Chemistry Group, Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281-S3, Gent 9000, Belgium
    • SCRiPTS Group, Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281-S3, Gent 9000, Belgium

    Search for more papers by this author
  • Patrick Bultinck,

    1. Ghent Quantum Chemistry Group, Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281-S3, Gent 9000, Belgium
    Search for more papers by this author
  • Isabel Van Driessche

    1. SCRiPTS Group, Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281-S3, Gent 9000, Belgium
    Search for more papers by this author

  • This article was published online on 24 August 2012. Errors were subsequently identified. This notice is included in the online and print versions to indicate that both have been corrected on 24 September 2012.

Abstract

In this work, a method is described to extend the iterative Hirshfeld-I method, generally used for molecules, to periodic systems. The implementation makes use of precalculated pseudopotential-based electron density distributions, and it is shown that high-quality results are obtained for both molecules and solids, such as ceria, diamond, and graphite. The use of grids containing (precalculated) electron densities makes the implementation independent of the solid state or quantum chemical code used for studying the system. The extension described here allows for easy calculation of atomic charges and charge transfer in periodic and bulk systems. The conceptual issue of obtaining reference densities for anions is discussed, and the delocalization problem for anionic reference densities originating from the use of a plane wave basis set is identified and handled. © 2012 Wiley Periodicals, Inc.

Ancillary