The free energy of a liquid when viewed as a population of overlapping clusters
Résumé
The expression of the free energy of a liquid in terms of an explicit decomposition of the particle configurations into local coordination clusters is examined. We argue that the major contribution to the entropy associated with structural fluctuations arises from the local athermal constraints imposed by the overlap of adjacent coordination shells. In the context of the recently developed Favoured Local Structure model [Soft Matt. 11, 3322 (2015)], we derive explicit expressions for the structural energy and entropy in the high temperature limit, compare this approximation with simulation data and consider the extension of this free energy to the case of spatial inhomogeneity in the distribution of local structures.