期刊
JOURNAL OF CHEMICAL PHYSICS
卷 143, 期 15, 页码 -出版社
AMER INST PHYSICS
DOI: 10.1063/1.4932539
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资金
- Conacyt [155698, 237045, 128369]
- NSERC
We extend the definition of the electronic chemical potential (mu(e)) and chemical hardness (eta(e)) to finite temperatures by considering a reactive chemical species as a true open system to the exchange of electrons, working exclusively within the framework of the grand canonical ensemble. As in the zero temperature derivation of these descriptors, the response of a chemical reagent to electron-transfer is determined by the response of the (average) electronic energy of the system, and not by intrinsic thermodynamic properties like the chemical potential of the electron-reservoir which is, in general, different from the electronic chemical potential, mu(e). Although the dependence of the electronic energy on electron number qualitatively resembles the piecewise-continuous straight-line profile for low electronic temperatures (up to ca. 5000 K), the introduction of the temperature as a free variable smoothens this profile, so that derivatives (of all orders) of the average electronic energy with respect to the average electron number exist and can be evaluated analytically. Assuming a three-state ensemble, well-known results for the electronic chemical potential at negative (-I), positive (-A), and zero values of the fractional charge (-(I + A)/2) are recovered. Similarly, in the zero temperature limit, the chemical hardness is formally expressed as a Dirac delta function in the particle number and satisfies the well-known reciprocity relation with the global softness. (C) 2015 AIP Publishing LLC.
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