A cavitation transition in the energy landscape of simple cohesive liquids and glasses
YE Altabet and FH Stillinger and PG Debenedetti, JOURNAL OF CHEMICAL PHYSICS, 145, 211905 (2016).
In particle systems with cohesive interactions, the pressure-density relationship of the mechanically stable inherent structures sampled along a liquid isotherm (i.e., the equation of state of an energy landscape) will display a minimum at the Sastry density rho S. The tensile limit at rho S is due to cavitation that occurs upon energy minimization, and previous characterizations of this behavior suggested that rho S is a spinodal-like limit that separates all homogeneous and fractured inherent structures. Here, we revisit the phenomenology of Sastry behavior and find that it is subject to considerable finite-size effects, and the development of the inherent structure equation of state with system size is consistent with the finite-size rounding of an athermal phase transition. What appears to be a continuous spinodal-like point at finite system sizes becomes discontinuous in the thermodynamic limit, indicating behavior akin to a phase transition. We also study cavitation in glassy packings subjected to athermal expansion. Many individual expansion trajectories averaged together produce a smooth equation of state, which we find also exhibits features of finite-size rounding, and the examples studied in this work give rise to a larger limiting tension than for the corresponding landscape equation of state. Published by AIP Publishing.
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