Entropy, local order, and the freezing transition in Morse liquids

Abstract

The behavior of the excess entropy of Morse and Lennard-Jones liquids is examined as a function of temperature, density, and the structural order metrics. The dominant pair correlation contribution to the excess entropy is estimated from simulation data for the radial distribution function. The pair correlation entropy (S₂) of these simple liquids is shown to have a threshold value of (-3.5±0.3)k_B at freezing. Moreover, S₂ shows a T^-2/5 temperature dependence. The temperature dependence of the pair correlation entropy as well as the behavior at freezing closely correspond to earlier predictions, based on density functional theory, for the excess entropy of repulsive inverse power and Yukawa potentials [Rosenfeld, Phys. Rev. E 62, 7524 (2000)]. The correlation between the pair correlation entropy and the local translational and bond orientational order parameters is examined, and, in the case of the bond orientational order, is shown to be sensitive to the definition of the nearest neighbors. The order map between translational and bond orientational order for Morse liquids and solids shows a very similar pattern to that seen in Lennard-Jones-type systems.