First-order phase transitions from poles in asymptotic representations of partition functions

Phys Rev E Stat Nonlin Soft Matter Phys. 2010 Mar;81(3 Pt 1):030101. doi: 10.1103/PhysRevE.81.030101. Epub 2010 Mar 23.

Abstract

Although partition functions of finite-size systems are always analytic, and hence have no poles, they can be expressed in many cases as series containing terms with poles. Here we show that such poles can be related to linear branches of the entropy, expressed in the thermodynamic limit as a function of the energy per particle. We also show that these poles can be used to determine whether the entropy is nonconcave or has linear parts, which is something that cannot be done with the sole knowledge of the thermodynamic free energy derived from the partition function. We discuss applications for equilibrium systems having first-order phase transitions.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Computer Simulation
  • Models, Chemical*
  • Phase Transition*
  • Thermodynamics