The dependence on and continuity of the energy and other molecular properties with respect to the number of electrons

被引:219
作者
Ayers, Paul W. [1 ]
机构
[1] McMaster Univ, Dept Chem, Hamilton, ON L8S 4M1, Canada
基金
加拿大自然科学与工程研究理事会;
关键词
zero-temperature grand canonical ensemble; derivative discontinuity; conceptual density functional theory; chemical reactivity;
D O I
10.1007/s10910-006-9195-5
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
It was recently shown that the size consistency of the energy implies that, for any system with a rational number of electrons, the energy is given by the weighted average of the two systems with the nearest integer numbers of electrons. Specifically, E[N+P/Q] = (1-P/Q)E[N] + (P/Q)E[N+1]. This paper extends that analysis, showing that the same result holds for irrational numbers of electrons. This proves that the energy is a continuous function of the number of electrons, and justifies differentiation with respect to electron number, providing a rigorous justification or the density-functional theoretic approaches to chemical concepts like the electronegativity and the Fukui function. Similar results hold for properties other than the energy. Specific emphasis is placed on molecular response properties associated with the density-functional theory of chemical reactivity.
引用
收藏
页码:285 / 303
页数:19
相关论文
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