How pervasive is the Hirshfeld partitioning?
One can partition the molecular density into its atomic contributions by minimizing the divergence of the atom-in-molecule densities from their corresponding reference pro-atomic densities, subject to the constraint that the sum of the atom-in-molecule densities is the total molecular density. We expose conditions on the divergence measure that are necessary, and sufficient, to recover the popular Hirshfeld partitioning. Specifically, among all local measures of the divergence between two probability distribution functions, the Hirshfeld partitioning is obtained only for f-divergences.
- Department of Chemistry and Chemical Biology, McMaster University, Hamilton, Ontario L8S 4M1 (Canada)
- Publication Date:
- OSTI Identifier:
- Resource Type:
- Journal Article
- Resource Relation:
- Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 4; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
- Country of Publication:
- United States
- 74 ATOMIC AND MOLECULAR PHYSICS; ATOMS; DENSITY; DISTRIBUTION FUNCTIONS; LIMITING VALUES; MOLECULES; PARTITION; PROBABILITY