TY - JOUR
T1 - Cavitation transition in the energy landscape
T2 - Distinct tensile yielding behavior in strongly and weakly attractive systems
AU - Altabet, Y. Elia
AU - Fenley, Andreia L.
AU - Stillinger, Frank H.
AU - Debenedetti, Pablo G.
N1 - Publisher Copyright:
© 2018 Author(s).
PY - 2018/3/21
Y1 - 2018/3/21
N2 - Particles with cohesive interactions display a tensile instability in the energy landscape at the Sastry density ρS. The signature of this tensile limit is a minimum in the landscape equation of state, the pressure-density relationship of inherent structures sampled along a liquid isotherm. Our previous work [Y. E. Altabet, F. H. Stillinger, and P. G. Debenedetti, J. Chem. Phys. 145, 211905 (2016)] revisited the phenomenology of Sastry behavior and found that the evolution of the landscape equation of state with system size for particles with interactions typical of molecular liquids indicates the presence of an athermal first-order phase transition between homogeneous and fractured inherent structures, the latter containing several large voids. Here, we study how this tensile limit manifests itself for different interparticle cohesive strengths and identify two distinct regimes. Particles with sufficiently strong cohesion display an athermal first-order phase transition, consistent with our prior characterization. Weak cohesion also displays a tensile instability. However, the landscape equation of state for this regime is independent of system size, suggesting the absence of a first-order phase transition. An analysis of the voids suggests that yielding in the energy landscape of weakly cohesive systems is associated with the emergence of a highly interconnected network of small voids. While strongly cohesive systems transition from exclusively homogeneous to exclusively fractured configurations at ρS in the thermodynamic limit, this interconnected network develops gradually, starting at ρS, even at infinite system size.
AB - Particles with cohesive interactions display a tensile instability in the energy landscape at the Sastry density ρS. The signature of this tensile limit is a minimum in the landscape equation of state, the pressure-density relationship of inherent structures sampled along a liquid isotherm. Our previous work [Y. E. Altabet, F. H. Stillinger, and P. G. Debenedetti, J. Chem. Phys. 145, 211905 (2016)] revisited the phenomenology of Sastry behavior and found that the evolution of the landscape equation of state with system size for particles with interactions typical of molecular liquids indicates the presence of an athermal first-order phase transition between homogeneous and fractured inherent structures, the latter containing several large voids. Here, we study how this tensile limit manifests itself for different interparticle cohesive strengths and identify two distinct regimes. Particles with sufficiently strong cohesion display an athermal first-order phase transition, consistent with our prior characterization. Weak cohesion also displays a tensile instability. However, the landscape equation of state for this regime is independent of system size, suggesting the absence of a first-order phase transition. An analysis of the voids suggests that yielding in the energy landscape of weakly cohesive systems is associated with the emergence of a highly interconnected network of small voids. While strongly cohesive systems transition from exclusively homogeneous to exclusively fractured configurations at ρS in the thermodynamic limit, this interconnected network develops gradually, starting at ρS, even at infinite system size.
UR - http://www.scopus.com/inward/record.url?scp=85044052057&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85044052057&partnerID=8YFLogxK
U2 - 10.1063/1.5019274
DO - 10.1063/1.5019274
M3 - Article
C2 - 29566513
AN - SCOPUS:85044052057
SN - 0021-9606
VL - 148
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 11
M1 - 114501
ER -