Non-Gaussian particle number fluctuations in vicinity of the critical point for van der Waals equation of state

Abstract

The non-Gaussian measures of the particle number fluctuations – skewness $S\sigma$ and kurtosis $\kappa \sigma^2$ – are calculated in a vicinity of the critical point. This point corresponds to the end point of the first-order liquid-gas phase transition. The gaseous phase is characterized by the positive values of skewness while the liquid phase has negative skew. The kurtosis appears to be significantly negative at the critical density and supercritical temperatures. The skewness and kurtosis diverge at the critical point. The classical van der Waals equation of state in the grand canonical ensemble formulation is used in our studies. Neglecting effects of the quantum statistics we succeed to obtain the analytical expressions for the rich structures of the skewness and kurtosis in a wide region around the critical point. These results have universal form, i.e., they do not depend on particular values of the van der Waals parameters $a$ and $b$. The strongly intensive measures of particle number and energy fluctuations are also considered and show singular behavior in the vicinity of the critical point.

Publication
Journal of Physics A 49, 015003 (2016)