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

Abstract

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. Throughout the past century great effort was devoted to the investigation of the physics of fluid systems: all of their thermodynamical properties in the phase diagram below the critical point are nowadays well known 3. On the other hand, experimental studies in the supercritical region have been limited so far, owing to technical difficulties. The fluid pressure-temperature (P-T) phase diagram includes a subcritical region with two different phases (liquid and gas, separated by the liquid-vapour coexistence line) and a single-phase supercritical region. Structural and dynamical investigations, aiming to extend the study of the fluid phase diagram well beyond the critical point play a crucial role in many fundamental and applied research fields, such as condensedmatter physics, Earth and planetary science, nanotechnology and waste management 4-8. From an experimental point of view, the challenge is to close the gap between studies on fluid and solid phases using diamond anvil cell (DAC) techniques 9-12 and studies on hot dense fluids by shock waves 13,14. As this gap typically overlaps with the supercritical fluid region, it is crucial to track the evolution of transport properties of fluids beyond the critical point. In the specific case of acoustic waves, most of the liquids show the so-called positive dispersion. This is an increase of the speed of sound as a function of wavelength from the continuum limit (λ → ∞)-in which the acoustic waves propagate adiabatically-to the short-wavelength limit, that is, on approaching the interparticle distances 15-17. The ultimate origin of this effect can be traced back to the presence of one (or more)

Similarity law for Widom lines and coexistence lines

“…Nonetheless, our understanding of these thermodynamic states is still limited: it has become clear that the notion of the supercritical state-space as a featureless domain has to be revised: Experiments show that in extension to the subcritical coexistence line (CL), there exists a supercritical crossover line across which fluid properties change continuously from a liquid-like to a gas-like state over a small temperature interval [7][8][9][10]. It coincides conceptually with the so-called Widom line, originally introduced by Stanley and colleagues [11,12] as the locus of the maximum correlation length.…”

Widom line and dynamical crossovers as routes to understand supercritical water

“…The WL of supercritical noble gases, Lennard-Jones and van der Waals fluids was recently studied by experiments and simulations [23][24][25][26][27] . In particular, a recent experimental work has paved the way to a more profound knowledge of hot dense fluids by detecting a crossover in sound velocity of supercritical fluids of noble gases connected to the WL 26 .…”

“…In particular, a recent experimental work has paved the way to a more profound knowledge of hot dense fluids by detecting a crossover in sound velocity of supercritical fluids of noble gases connected to the WL 26 .…”

Nanosized objects in equilibrium supercritical fluids

“…This line may be traced also by peaks of some other thermophysical properties, especially, the constant pressure heat capacity [9,10]. In many works this peak line is named as the Widom line [11,12]. This line divides the supercritical zone into two regions that "can be identified by different dynamical regimes: gas-like and liquid-like" [12].…”