Journal of Mathematical Chemistry

, Volume 43, Issue 1, pp 285–303 | Cite as

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

  • Paul W. AyersEmail author

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.


zero-temperature grand canonical ensemble derivative discontinuity conceptual density functional theory chemical reactivity 


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Copyright information

© Springer Science+Business Media, LLC 2006

Authors and Affiliations

  1. 1.Department of ChemistryMcMaster UniversityHamiltonCanada

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