Phase transitions in “small” systems

Abstract

Traditionally, phase transitions are defined in the thermodynamic limit only. We discuss how phase transitions of first order (with phase separation and surface tension), continuous transitions and (multi)-critical points can be seen and classified for small systems. Boltzmann defines the entropy as the logarithm of the area W(E,N)=e^S(E,N) of the surface in the mechanical N-body phase space at total energy E. The topology of the curvature determinant D(E,N) of S(E,N) allows the classification of phase transitions without taking the thermodynamic limit. The first calculation of the entire entropy surface S(E,N) for the diluted Potts model (ordinary (q=3)-Potts model plus vacancies) on a 50*50 square lattice is shown. The regions in {E,N} where D>0 correspond to pure phases, ordered resp. disordered, and D<0 represent transitions of first order with phase separation and ``surface tension''. These regions are bordered by a line with D=0. A line of continuous transitions starts at the critical point of the ordinary (q=3)-Potts model and runs down to a branching point P_m. Along this line \nabla D vanishes in the direction of the eigenvector v_1 of D with the largest eigen-value \lambda_1\approx 0. It characterizes a maximum of the largest eigenvalue \lambda_1. This corresponds to a critical line where the transition is continuous and the surface tension disappears. Here the neighboring phases are indistinguishable. The region where two or more lines with D=0 cross is the region of the (multi)-critical point. The micro-canonical ensemble allows to put these phenomena entirely on the level of mechanics.