Communication: system-size scaling of Boltzmann and alternate Gibbs entropies.

J Chem Phys

Departament de Fisica Fonamental, Universitat de Barcelona, Diagonal 647, 08028 Barcelona, Spain.

Published: May 2014

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Article Abstract

It has recurrently been proposed that the Boltzmann textbook definition of entropy S(E) = k ln Ω(E) in terms of the number of microstates Ω(E) with energy E should be replaced by the expression S(G)(E) = k ln Σ(E' < E)Ω(E') examined by Gibbs. Here, we show that SG either is equivalent to S in the macroscopic limit or becomes independent of the energy exponentially fast as the system size increases. The resulting exponential scaling makes the realistic use of SG unfeasible and leads in general to temperatures that are inconsistent with the notions of hot and cold.

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http://dx.doi.org/10.1063/1.4879553DOI Listing

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