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Title
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An extension of the Hirshfeld method to open shell systems using fractional occupations
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Author
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Abstract
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| 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. |
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Language
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English
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Source (journal)
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Journal of chemical theory and computation. - -
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Publication
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2011
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ISSN
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1549-9618
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DOI
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10.1021/CT100743H
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Volume/pages
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7
:5
(2011)
, p. 1328-1335
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ISI
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000290293000011
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Full text (Publisher's DOI)
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