期刊
PHYSICAL REVIEW E
卷 103, 期 5, 页码 -出版社
AMER PHYSICAL SOC
DOI: 10.1103/PhysRevE.103.052102
关键词
-
资金
- NSF [CHE-1955403]
- National Science Foundation [ACI-1548562, TG-CHE200063]
Entropy has attracted interest as a marker for phase transitions and a reaction coordinate. The study focuses on entropy behavior along the vapor-liquid phase coexistence line in ideal and metallic systems, showing differences in entropy between coexisting phases. Systems with many-body effects show a departure from ideality and a greater variation in vaporization entropy with temperature near the critical temperature.
Entropy has recently drawn considerable interest both as a marker to detect the onset of phase transitions and as a reaction coordinate, or collective variable, to span phase transition pathways. We focus here on the behavior of entropy along the vapor-liquid phase coexistence and identify how the difference in entropy between the two coexisting phases vary in ideal and metallic systems along the coexistence curve. Using flat-histogram simulations, we determine the thermodynamic conditions of coexistence, critical parameters, including the critical entropy, and entropies along the binodal. We then apply our analysis to a series of systems that increasingly depart from ideality and adopt a metal-like character, through the gradual onset of the Friedel oscillation in an effective pair potential, and for a series of transition metals modeled with a many-body embedded-atoms force field. Projections of the phase boundary on the entropy-pressure and entropy-temperature planes exhibit two qualitatively different behaviors. While all systems modeled with an effective pair potential lead to an ideal-like behavior, the onset of many-body effects results in a departure from ideality and a markedly greater exponent for the variation of the entropy of vaporization with temperature away from the critical temperature.
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