Thermodynamic theory of equilibrium fluctuations

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dc.contributor.authorMishin, Y.
dc.date.accessioned2016-08-09T00:11:06Z
dc.date.available2016-08-09T00:11:06Z
dc.date.issued2015-09-25
dc.description.abstractThe postulational basis of classical thermodynamics has been expanded to incorporate equilibrium fluctuations. The main additional elements of the proposed thermodynamic theory are the concept of quasi-equilibrium states, a definition of non-equilibrium entropy, a fundamental equation of state in the entropy representation, and a fluctuation postulate describing the probability distribution of macroscopic parameters of an isolated system. Although these elements introduce a statistical component that does not exist in classical thermodynamics, the logical structure of the theory is different from that of statistical mechanics and represents an expanded version of thermodynamics. Based on this theory, we present a regular procedure for calculations of equilibrium fluctuations of extensive parameters, intensive parameters and densities in systems with any number of fluctuating parameters. The proposed fluctuation formalism is demonstrated by four applications: (1) derivation of the complete set of fluctuation relations for a simple fluid in three different ensembles; (2) fluctuations in finite-reservoir systems interpolating between the canonical and micro-canonical ensembles; (3) derivation of fluctuation relations for excess properties of grain boundaries in binary solid solutions, and (4) derivation of the grain boundary width distribution for pre-melted grain boundaries in alloys. The last two applications offer an efficient fluctuation-based approach to calculations of interface excess properties and extraction of the disjoining potential in pre-melted grain boundaries. Possible future extensions of the theory are outlined.
dc.description.sponsorshipThis work was supported by the National Science Foundation, Division of Materials Research, the Metals and Metallic Nanostructures Program, grant number 1308667. Publication of this article was funded in part by the George Mason University Libraries Open Access Publishing Fund.
dc.identifier.citationMishin, Y. “Thermodynamic Theory of Equilibrium Fluctuations.” Annals of Physics 363 (December 2015): 48–97. doi:10.1016/j.aop.2015.09.015.
dc.identifier.doihttp://dx.doi.org/10.1016/j.aop.2015.09.015
dc.identifier.urihttps://hdl.handle.net/1920/10333
dc.language.isoen_US
dc.publisherElsevier
dc.subjectThermodynamics
dc.subjectFluctuation
dc.subjectEntropy
dc.subjectGrain boundary
dc.subjectPre-melting
dc.titleThermodynamic theory of equilibrium fluctuations
dc.typeArticle

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