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Average electronic energy is the central quantity in conceptual chemical reactivity theory

Content Provider	Springer Nature Link
Author	Franco Pérez, Marco Ayers, Paul W. Gázquez, José L.
Copyright Year	2016
Abstract	We show that, at both zero and nonzero temperature, the average electronic energy is the central quantity for the study of chemical reactivity using density functional theory. Specifically, we show that regardless of the temperature and the ensemble framework one chooses, the average electronic energy exhibits the functional dependence with respect to external potential and electron number of the zero-temperature case, but with the presence of an additional temperature-dependent term that vanishes in the zero-temperature limit. This reconciles the results from the finite-temperature chemical reactivity theory with those of the traditional zero-temperature approach, and resolves apparent discrepancies between the canonical and grand canonical ensembles. However, the grand canonical ensemble provides a more convenient mathematical framework for studying chemical reactivity because it regards chemical species as open quantum (sub)systems. The response functions of the average electronic energy reduce to the zero-temperature reactivity descriptors in the appropriate limit, helping to justify the use of idealized zero-temperature approximations for describing experimental results obtained at nonzero temperature. Extending this approach to the entropy, the responses of the entropy are shown to give a different set of interesting chemical reactivity response functions. The expressions for the heat capacity of an electronic system are especially elucidative.
Starting Page	1
Ending Page	8
Page Count	8
File Format	PDF
ISSN	1432881X
Journal	Theoretical Chemistry Accounts
Volume Number	135
Issue Number	8
e-ISSN	14322234
Language	English
Publisher	Springer Berlin Heidelberg
Publisher Date	2016-07-30
Publisher Place	Berlin, Heidelberg
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Density functional theory for chemical reactivity Thermodynamic state functions Grand canonical ensemble Electronic heat capacity Chemical concepts Electronic entropy Theoretical and Computational Chemistry Inorganic Chemistry Organic Chemistry Physical Chemistry Atomic/Molecular Structure and Spectra
Content Type	Text
Resource Type	Article
Subject	Physical and Theoretical Chemistry

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