Equipartition theorem and the dynamics of liquids

Abstract

In liquids, phonons have a very short lifetime and the total potential energy does not depend linearly on temperature. Thus it may appear that atomic vibrations in liquids cannot be described by the harmonic-oscillator model and that the equipartition theorem for the potential energy is not upheld. In this paper we show that the description of the local atomic dynamics in terms of the atomic-level stresses provides such a description, satisfying the equipartition theorem. To prove this point we carried out molecular-dynamics simulations with several pairwise potentials, including the Lennard-Jones potential, the modified Johnson potential, and the repulsive part of the Johnson potential, at various particle number densities. In all cases studied the total self-energy of the atomic-level stresses followed the $(3/2){k}_{B}T$ law. From these results we suggest that the concept of local atomic stresses can provide description of thermodynamic properties of glasses and liquids on the basis of harmonic atomistic excitations. An example of application of this approach to the description of the glass transition temperature in metallic glasses is discussed.