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

Abstract

The Ruppeiner geometry has been shown to provide novel ways for constructing the phase boundaries and the Widom line of certain fluids. This paper examines the applicability of these geometric constructions to more general fluids. We develop a general equation-of-state expansion for fluids near a critical point that mainly assumes analyticity with respect to the number density. Based on this general parametrization of fluids, we prove the equivalence of the Ruppeiner geometric construction and the standard Maxwell construction of phase boundaries near the critical point. In contrast, we find that the usual prescription based on the Ruppeiner geometry for the Widom line does not produce the expected Widom line for arbitrary cases of our general fluid equationof state. This usual prescription relies on the Ruppeiner metric induced on a particular hypersurface of the thermodynamic manifold. We show that by choosing a different hypersurface, which we call the Ruppeiner-N surface, and using its associated induced metric, the Ruppeiner construction generates the entire Widom line of the van der Waals fluid exactly, even away from the critical point. Interestingly, this alternative hypersurface yields another benefit. It improves the classification scheme originally proposed by Diósi etal. for partitioning the van der Waals state space into its different phases using geodesics of a thermodynamic metric. We argue that, whereas the original Diósi boundaries did not correspond to any clear thermodynamic lines, the corresponding boundaries based on the Ruppeiner-N metric become sensitive to the presence of the van der Waals Widom line and provide the correct classification of all van der Waals states. These results suggest that the Ruppeiner-N surface may be the more appropriate hypersurface to use when studying phase diagrams with thermodynamic geometry.