Journal
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
Volume 109, Issue 9, Pages 1790-1806Publisher
WILEY
DOI: 10.1002/qua.21901
Keywords
Hirshfeld population analysis (HPA); Fukui function; atom in a molecule (AIM); deformation density; information theoretic foundation
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Funding
- Department of Science and Technology (DST) [SR/S1/PC-28/2004]
- University Grants Comission (UGC)
- Special Assistance Programme (SAP), India [540/14/DRS/2007]
- NSERC
- Canada Research Chairs, Sharcnet, Alfred P. Sloan foundation
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In the present article, we report a comparative study between the Hirshfeld and Mulliken population analysis schemes (abbreviated as HPA and MPA, respectively). Trends of atomic charges derived from these two population analysis schemes are compared with those expected from other commonly used chemical concepts like electronegativity, inductive effects, and resonance effects. Although previous studies on intramolecular reactivity sequences demonstrated that HPA generates reliable and non-negative (and thus physically more realistic) condensed Fukui function (FF) values, the present study reveals problems with the HPA charge partitioning technique. Specifically, HPA fails to reproduce reliable intermolecular and intramolecular charge trends in several systems. Reasons for the success and failure of HPA are discussed and a method for improving the Hirshfeld charge partitioning is proposed. (c) 2008 Wiley Periodicals, Inc. Int J Quantum Chem 109: 1790-1806, 2009
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