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Electrostatic Free Energy and Other Properties of States Having Nonequilibrium Polarization. I

Marcus, R. A. (1956) Electrostatic Free Energy and Other Properties of States Having Nonequilibrium Polarization. I. Journal of Chemical Physics, 24 (5). pp. 979-989. ISSN 0021-9606. doi:10.1063/1.1742724. https://resolver.caltech.edu/CaltechAUTHORS:20140505-104019660

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Abstract

Various processes such as electron transferreactions, redox reactions at electrodes, and electronic excitation of dissolved ions may proceed by way of intermediate states whose electrical polarization is not in equilibrium with the field arising from the charges present. The usual expressions for the electrostatic-free energy and for the differential equation satisfied by the potential assume that the polarization and the field are in equilibrium. Accordingly, these equations are of but limited applicability to these processes. In the present paper equations are derived for various properties of systems having such nonequilibrium electrostatic configurations. These properties include the free energy, energy, and entropy of the nonequilibrium system, and the spacial dependence of the electrostatic potential. The free energy, for example, will be used to calculate the probability of formation of nonequilibrium states in certain problems of physical interest.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1063/1.1742724DOIArticle
http://scitation.aip.org/content/aip/journal/jcp/24/5/10.1063/1.1742724PublisherArticle
ORCID:
AuthorORCID
Marcus, R. A.0000-0001-6547-1469
Additional Information:© 1956 American Institute of Physics. Received July 11, 1955. This research was supported by the Office of Naval Research under Contract No. Nonr 839(09). Reproduction in whole or in part is permitted for any purpose of the United States Government.
Funders:
Funding AgencyGrant Number
Office of Naval Research (ONR)Nonr 839(09)
Subject Keywords:Electrostatics; Free energy; Polarization; Redox; Charge transfer
Issue or Number:5
DOI:10.1063/1.1742724
Record Number:CaltechAUTHORS:20140505-104019660
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20140505-104019660
Official Citation:Marcus, R. A. (1956). Electrostatic Free Energy and Other Properties of States Having Nonequilibrium Polarization. I. The Journal of Chemical Physics, 24(5), 979-989. doi: doi:http://dx.doi.org/10.1063/1.1742724
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:45494
Collection:CaltechAUTHORS
Deposited By:INVALID USER
Deposited On:05 May 2014 17:49
Last Modified:10 Nov 2021 17:04

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