Complex phase diagram and supercritical matter.

Abstract

The supercritical region is often described as uniform with no definite transitions. The distinct behaviors of the matter therein, e.g., as liquidlike and gaslike, however, suggest "supercritical boundaries." Here we provide a mathematical description of these phenomena by revisiting the Yang-Lee theory and introducing a complex phase diagram, specifically a four-dimensional (4D) one with complex T and p. While the traditional 2D phase diagram with real temperature T and pressure p values (the physical plane) lacks Lee-Yang (LY) zeros beyond the critical point, preventing the occurrence of criticality, the off-plane zeros in this 4D scenario still induce critical anomalies in various physical properties. This relationship is evidenced by the correlation between the Widom line and LY edges in van der Waals, 2D Ising model, and water. The diverged supercritical boundaries manifest the high-dimensional feature of the phase diagram: e.g., when LY zeros of complex T or p are projected onto the physical plane, boundaries defined by isobaric heat capacity C_{p} or isothermal compression coefficient K_{T} emanates. These results demonstrate the incipient phase transition nature of the supercritical matter.