超临界物质的热力学行为
Thermodynamic behavior of supercritical matter
摘要：
自1822年发现以来，超临界流体一直受到人们的关注，并已开始在许多重要应用中部署。对超临界状态的理论理解是缺乏的，并且被认为限制了进一步的工业部署。在这里，我们研究了超临界状态的热力学性质，并发现比热显示出两个不同的制度之间的交叉，一个意想不到的结果，鉴于目前认为超临界状态的物理性质方面的均匀性。随后，我们制定了系统热力学理论以上的交叉，并找到良好的协议计算和实验比热没有自由拟合参数。我们推导出一个幂律和分析超临界标度指数的系统以上的弗伦克尔线。在该理论中，能量和热容仅由系统中纵向模式的最小长度决定，并且不明确地取决于系统特定的结构和相互作用。
英文摘要：
Since their discovery in 1822, supercritical fluids have been of enduring interest, and have started to be deployed in many important applications. Theoretical understanding of the supercritical state is lacking, and is seen to limit further industrial deployment. Here, we study thermodynamic properties of the supercritical state, and discover that specific heat shows a crossover between two different regimes, an unexpected result in view of currently perceived homogeneity of supercritical state in terms of physical properties. We subsequently formulate a theory of system thermodynamics above the crossover, and find good agreement between calculated and experimental specific heat with no free fitting parameters. We derive a power law and analyze supercritical scaling exponents in the system above the Frenkel line. In this theory, energy and heat capacity are governed by the minimal length of the longitudinal mode in the system only, and do not explicitly depend on system-specific structure and interactions.
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