Dima Bolmatov, V. V. Brazhkin, K. Trachenko
Properties of supercritical fluids have been of enduring interest since the critical phenomena were discovered by Cagniard de la Tour in 1822, stimulating fundamental theoretical work and development of experimental techniques. Here, we study the thermodynamic properties of the supercritical state, and discover that specific heat shows a crossover between two different dynamic regimes of the low-temperature rigid liquid and high-temperature non-rigid supercritical fluid. We formulate a theory of heat capacity above the crossover, and find good agreement between calculated and experimental data for rare-gas supercritical liquids (Ne, Ar, Kr and Xe) with no free fitting parameters. We derive the relationship between scaling exponents of heat capacity and viscosity in the supercritical region, and show that these exponents exhibit universality. The universality is explained by the universal temperature behavior of the maximal length of the longitudinal phonons that can exist in the supercritical system and that is not sensitive to system details.
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http://arxiv.org/abs/1303.3153
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