An extension of the Hirshfeld method to open shell systems using fractional occupations

D. Geldof, A. Krishtal, F. Blockhuys, C. Van Alsenoy

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Abstract

In this work, a new partitioning method is presented which allows one to calculate properties of radicals, in particular, atomic spin populations. The method can be seen as an extension of the Hirshfeld-I method [Bultinck, P. et al. J. Chem. Phys. 2007, 126, 144111 ], in which the atomic weight functions, defining the atoms-in-molecules, are constructed by means of an iterative scheme in which the charges of the atoms-in-molecules are altered but the spin remains fixed. The Hirshfeld-I method is therefore not suitable for the calculation of atomic spin populations of open-shell systems. The new fractional occupation Hirshfeld-I (FOHI) uses an iterative scheme in which both the atomic charge and spin are optimized, resulting in a self-consistent method for the calculation of atomic spin populations. The results obtained with the FOHI method are compared with experimental results obtained using polarized neutron diffraction, thus serving as a validation of the FOHI method as well as the Hirshfeld definition of atoms-in-molecules in general.

Original languageEnglish (US)
Pages (from-to)1328-1335
Number of pages8
JournalJournal of Chemical Theory and Computation
Volume7
Issue number5
DOIs
StatePublished - May 10 2011
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Computer Science Applications
  • Physical and Theoretical Chemistry

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