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Abstract
We develop an approach to liquid thermodynamics based on collective modes. We perform extensive molecular-dynamics simulations of noble, molecular, and metallic liquids, and we provide direct evidence that liquid energy and specific heat are well-described by the temperature dependence of the Frenkel (hopping) frequency. The agreement between predicted and calculated thermodynamic properties is seen in the notably wide range of temperature spanning tens of thousands of Kelvin. The range includes both subcritical liquids and supercritical fluids. We discuss the structural crossover and interrelationships between the structure, dynamics, and thermodynamics of liquids and supercritical fluids.
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