Title
An extension of the Hirshfeld method to open shell systems using fractional occupations An extension of the Hirshfeld method to open shell systems using fractional occupations
Author
Faculty/Department
Faculty of Sciences. Chemistry
Publication type
article
Publication
Subject
Physics
Chemistry
Source (journal)
Journal of chemical theory and computation
Volume/pages
7(2011) :5 , p. 1328-1335
ISSN
1549-9618
ISI
000290293000011
Carrier
E
Target language
English (eng)
Full text (Publishers DOI)
Affiliation
University of Antwerp
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.
E-info
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