Thermodynamic geometry, phase transitions, and the Widom line.

A microscopic characterization, based on the thermodynamic curvature R, is proposed for first-order liquid-gas phase transitions. Near the critical point, where R is proportional to the correlation volume ξ(3), we propose that R takes the same value in the coexisting phases. This proposal allows a determination of the liquid-gas coexistence curve with no use of the problematic Maxwell equal area construction. Furthermore, |R| ~ ξ(3) allows a direct determination of the Widom line in the supercritical regime. We illustrate with input from the van der Waals model and the National Institute of Standards and Technology Chemistry WebBook.