Trond S. Ingebrigtsen, Arno A. Veldhorst, Thomas B. Schrøder, Jeppe C. Dyre
We investigate the accuracy of the expression of Rosenfeld and Tarazona (RT) for the excess isochoric heat capacity, C_V^{ex} \propto T^{-2/5}, for eighteen model liquids. Previous investigations have reported no unifying features of breakdown for the RT expression. Here liquids with different stoichiometric composition, molecular topology, chemical interactions, degree of undercooling, and environment are investigated. We find that the RT expression is a better approximation for liquids with strong correlations between equilibrium fluctuations of virial and potential energy, i.e., Roskilde simple liquids [Ingebrigtsen et al., Phys. Rev. X 2, 011011 (2012)]. This observation holds even for molecular liquids under severe nanoscale confinement, the physics of which is completely different from the original RT bulk hard-sphere fluid arguments. The density dependence of the specific heat is predicted from the isomorph theory for Roskilde simple liquids, which in combination with the RT expression provides a complete description of the specific heat's density and temperature dependence.
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http://arxiv.org/abs/1305.1776
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