The Widom line as the crossover between liquid-like and gas-like behaviour in supercritical fluids

By conventional definition, a supercritical fluid is one that doesn’t exhibit distinct liquid- or gas-like states. This may need to be revised in light of measurements that show a sharp change in the speed of sound in supercritical argon when it crosses a well-defined line on its pressure versus temperature phase diagram. According to textbook definitions 1 , there exists no physical observable able to distinguish a liquid from a gas beyond the critical point, and hence only a single fluid phase is defined. There are, however, some thermophysical quantities, having maxima that define a line emanating from the critical point, named ‘the Widom line’ 2 in the case of the constant-pressure specific heat. We determined the velocity of nanometric acoustic waves in supercritical fluid argon at high pressures by inelastic X-ray scattering and molecular dynamics simulations. Our study reveals a sharp transition on crossing the Widom line demonstrating how the supercritical region is actually divided into two regions that, although not connected by a first-order singularity, can be identified by different dynamical regimes: gas-like and liquid-like, reminiscent of the subcritical domains. These findings will pave the way to a deeper understanding of hot dense fluids, which are of paramount importance in fundamental and applied sciences.