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Are the Hirshfeld and Mulliken population analysis schemes consistent with chemical intuition?
Author(s) -
Saha Soumen,
Roy Ram Kinkar,
Ayers Paul W.
Publication year - 2008
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.21901
Subject(s) - intramolecular force , electronegativity , mulliken population analysis , intermolecular force , computational chemistry , chemistry , fukui function , atomic charge , charge (physics) , population , quantum chemical , chemical physics , quantum mechanics , physics , density functional theory , molecule , stereochemistry , organic chemistry , demography , electrophile , sociology , catalysis
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. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009