Coexistence in Finite Systems

David J. Wales and R. Stephen Berry
Phys. Rev. Lett. 73, 2875 – Published 21 November 1994
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Abstract

We derive necessary conditions for finite systems to exhibit two locally stable states with respect to fluctuations in the microcanonical and canonical ensembles. The requirements are, respectively, that there be two inflections in the logarithm of the probability distribution of the energy or the number of particles in the canonical or grand canonical ensembles. The thermodynamics associated with the whole phase space may be related to quantities averaged over regions of phase space and are consistent with van Hove's theorem.

  • Received 27 January 1994

DOI:https://doi.org/10.1103/PhysRevLett.73.2875

©1994 American Physical Society

Authors & Affiliations

David J. Wales

  • University Chemical Laboratories, Lensfield Road, Cambridge, CB2 1EW, United Kingdom

R. Stephen Berry

  • Department of Chemistry, University of Chicago, 5735 South Ellis Avenue, Chicago, Illinois 60637

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Vol. 73, Iss. 21 — 21 November 1994

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