Isomorph Invariance of Higher-Order Structural Measures in Four Lennard-Jones Systems.

In the condensed liquid phase, both single- and multicomponent Lennard-Jones (LJ) systems obey the "hidden-scale-invariance" symmetry to a good approximation. Defining an isomorph as a line of constant excess entropy in the thermodynamic phase diagram, the consequent approximate isomorph invariance of structure and dynamics in appropriate units is well documented. However, although all measures of the structure are predicted to be isomorph invariant, with few exceptions only the radial distribution function (RDF) has been investigated. This paper studies the variation along isomorphs of the nearest-neighbor geometry quantified by the occurrence of Voronoi structures, Frank-Kasper bonds, icosahedral local order, and bond-orientational order. Data are presented for the standard LJ system and for three binary LJ mixtures (Kob-Andersen, Wahnström, NiY2). We find that, while the nearest-neighbor geometry generally varies significantly throughout the phase diagram, good invariance is observed along the isomorphs. We conclude that higher-order structural correlations are no less isomorph invariant than is the RDF.

Distance-as-time in physical aging.

Although it has been known for half a century that the physical aging of glasses in experiments is described well by a linear thermal-history convolution integral over the so-called material time, the microscopic definition and interpretation of the material time remains a mystery. We propose that the material-time increase over a given time interval reflects the distance traveled by the system's particles. Different possible distance measures are discussed, starting from the standard mean-square displacement and its inherent-state version that excludes the vibrational contribution. The viewpoint adopted, which is inspired by and closely related to pioneering works of Cugliandolo and Kurchan from the 1990s, implies a "geometric reversibility" and a "unique-triangle property" characterizing the system's path in configuration space during aging. Both of these properties are inherited from equilibrium, and they are here confirmed by computer simulations of an aging binary Lennard-Jones system. Our simulations moreover show that the slow particles control the material time. This motivates a "dynamic-rigidity-percolation" picture of physical aging. The numerical data show that the material time is dominated by the slowest particles' inherent mean-square displacement, which is conveniently quantified by the inherent harmonic mean-square displacement. This distance measure collapses data for potential-energy aging well in the sense that the normalized relaxation functions following different temperature jumps are almost the same function of the material time. Finally, the standard Tool-Narayanaswamy linear material-time convolution-integral description of physical aging is derived from the assumption that when time is replaced by distance in the above sense, an aging system is described by the same expression as that of linear-response theory.