Determining landscape-based criteria for freezing of liquids

Abstract

The correlation between statistical properties of the energy landscape and the number of accessible configurational states, as measured by the exponential of the excess entropy (e(Se)), are studied in the case of a simple Lennard-Jones-type liquid in the neighborhood of the thermodynamic freezing transition. The excess entropy Se is defined as the difference between the entropy of the liquid and that of the ideal gas under identical temperature and pressure conditions and is estimated using the pair correlation contribution, S2. Landscape properties associated with three categories of configurations are considered: instantaneous configurations, inherent saddles, and inherent minima. Landscape properties studied include the energy and the key parameters of the Hessian eigenvalue distribution as well as the mean distances between instantaneous configurations and the corresponding inherent saddles and minima. The signatures of the thermodynamic freezing transition are clearest in the case of inherent structure properties which show, as a function of e(S2), a pronounced change in slope in the vicinity of the solid-liquid coexistence. The mean distance between instantaneous and saddle configurations also shows a similar change in slope when the system crosses from the stable to the supercooled regime. In the case of inherent saddles, the minimum eigenvalue acts as a similar indicator of the thermodynamic freezing transition but the average and maximum eigenvalues do not carry similar signatures. In the case of instantaneous configurations, a weak indicator of the thermodynamic freezing transition is seen in the behavior of the fraction of negative curvature directions as a function of the exponential of the excess entropy.