TY - JOUR

T1 - A cavitation transition in the energy landscape of simple cohesive liquids and glasses

AU - Altabet, Y. Elia

AU - Stillinger, Frank H.

AU - Debenedetti, Pablo G.

N1 - Funding Information:
gratefully acknowledges the support of the National Science Foundation (Grant No. CHE-1213343)
Publisher Copyright:
© 2016 Author(s).

PY - 2016/12/7

Y1 - 2016/12/7

N2 - 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 ρS. The tensile limit at ρS is due to cavitation that occurs upon energy minimization, and previous characterizations of this behavior suggested that ρS 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.

AB - 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 ρS. The tensile limit at ρS is due to cavitation that occurs upon energy minimization, and previous characterizations of this behavior suggested that ρS 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.

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U2 - 10.1063/1.4959846

DO - 10.1063/1.4959846

M3 - Article

C2 - 28799356

AN - SCOPUS:84980009961

VL - 145

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 21

M1 - 211905

ER -