Stability conditions for density functional reactivity theory: An interpretation of the total local hardness

被引：6

作者：

Ayers, Paul W. ^{[1
]}

Liu, Shubin ^{[2
]}

Li, Tonglei ^{[3
]}

机构：

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

[2] Univ N Carolina, Ctr Res Comp, Chapel Hill, NC 27599 USA

[3] Univ Kentucky, Dept Pharmaceut Sci, Lexington, KY 40536 USA

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2011年 / 13卷 / 10期

基金：

美国国家科学基金会; 加拿大自然科学与工程研究理事会;

关键词：

DESCRIBING CHEMICAL-REACTIONS; HARD/SOFT ACID/BASE PRINCIPLE; FRONTIER-ELECTRON THEORY; FUKUI FUNCTION; VARIATIONAL-PRINCIPLES; ABSOLUTE HARDNESS; EMPIRICAL ENERGY; GENERAL-PURPOSE; EXCHANGE; SOFTNESS;

D O I：

10.1039/c0cp01675f

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：

The second-order Taylor series expansions commonly used in the density functional chemical reactivity theory are used to define local stability conditions for electronic states. Systems which satisfy these conditions are stable to infinitesimal perturbations due to approaching chemical reagents. The basic formalism considered here supersedes previous variational approaches to chemical reactivity theory like the electrophilicity, potentialphilicity, and chargephilicity. The total local hardness emerges naturally in this analysis, and can be clearly interpreted. When the total local hardness is small, the system is relatively insensitive to perturbations. Furthermore, minus the total local hardness is an energetically favorable perturbation of the external potential.

引用

页码：4427 / 4433

页数：7

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