Decoding heat capacity features from the energy landscape.

Abstract

A general scheme is derived to connect transitions in configuration space with features in the heat capacity. A formulation in terms of occupation probabilities for local minima that define the potential energy landscape provides a quantitative description of how contributions arise from competition between different states. The theory does not rely on a structural interpretation for the local minima, so it is equally applicable to molecular energy landscapes and the landscapes defined by abstract functions. Applications are presented for low-temperature solid-solid transitions in atomic clusters, which involve just a few local minima with different morphologies, and for cluster melting, which is driven by the landscape entropy associated with the more numerous high-energy minima. Analyzing these features in terms of the balance between states with increasing and decreasing occupation probabilities provides a direct interpretation of the underlying transitions. This approach enables us to identify a qualitatively different transition that is caused by a single local minimum associated with an exceptionally large catchment volume in configuration space for a machine learning landscape.