Are the Hirshfeld and Mulliken Population Analysis Schemes Consistent With Chemical Intuition?

被引：115

作者：

Saha, Soumen ^{[1
]}

Roy, Ram Kinkar ^{[1
]}

Ayers, Paul W. ^{[2
]}

机构：

[1] BITS, Dept Chem, Pilani 333031, Rajasthan, India

[2] McMaster Univ, Dept Chem, Hamilton, ON L8S 4M1, Canada

来源：

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY | 2009年 / 109卷 / 09期

基金：

加拿大自然科学与工程研究理事会;

关键词：

Hirshfeld population analysis (HPA); Fukui function; atom in a molecule (AIM); deformation density; information theoretic foundation; DENSITY-FUNCTIONAL-APPROACH; FRONTIER-ELECTRON THEORY; FUKUI FUNCTION INDEXES; INFORMATION-THEORY; HYDRIDE ADDITION; NON-NEGATIVITY; BASIS-SETS; ATOMS; MOLECULES; ENERGY;

D O I：

10.1002/qua.21901

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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

引用

页码：1790 / 1806

页数：17

共 72 条

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