Phase boundaries and the Widom line from the Ruppeiner geometry of fluids

Abstract

In the study of fluid phases, the Ruppeiner geometry provides novel ways for constructing the phase boundaries (known as the $R$-crossing method) and the Widom line, which is considered by many to be the continuation of the coexistence curve beyond the critical point. In this paper, we revisit these geometry-based constructions with the aim of understanding their limitations and generality. We introduce a new equation-of-state expansion for fluids near a critical point, assuming analyticity with respect to the number density, and use this to prove a number of key results, including the equivalence between the $R$-crossing method and the standard construction of phase boundaries near the critical point. The same conclusion is not seen to hold for the Widom line of fluids in general. However, for the ideal van der Waals fluid a slight tweak in the usual formulation of the Ruppeiner metric, which we call the Ruppeiner-$N$ metric, makes the Ruppeiner geometry prediction of the Widom line exact. This is in contrast to the results of May and Mausbach where the prediction is good only up to the slope of the Widom line at the critical point. We also apply the Ruppeiner-$N$ metric to improve the proposed classification scheme of Diósi et al. that partitions the van der Waals state space into its different phases using Ruppeiner geodesics. Whereas the original Diósi boundaries do not correspond to any established thermodynamic lines above (or even below) the critical point, our construction remarkably detects the Widom line. These results suggest that the Ruppeiner-$N$ metric may play a more important role in thermodynamic geometry than is presently appreciated.