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Title: Microscopic theory of onset of decaging and bond-breaking activated dynamics in ultradense fluids with strong short-range attractions

Abstract

We theoretically study thermally activated “in cage” elementary dynamical processes that precede full structural relaxation in ultra-dense particle liquids interacting via strong short range attractive forces. The analysis is based on a microscopic theory formulated at the particle trajectory level built on the dynamic free energy concept and an explicit treatment of how attractive forces control the formation and lifetime of physical bonds. Mean time scales for bond breaking, the early stage of cage escape, and non-Fickian displacement by a fixed amount are analyzed in the repulsive glass, bonded repulsive (attractive) glass, fluid, and dense gel regimes. The theory predicts a strong length-scale-dependent growth of these time scales with attractive force strength at fixed packing fraction, a much weaker slowing down with density at fixed attraction strength, and a strong decoupling of the shorter bond breaking time with the other two time scales that are controlled mainly by perturbed steric caging. All results are in good accord with simulations, and additional testable predictions are made. In conclusion, the classic statistical mechanical projection approximation of replacing all bare attractive and repulsive forces with a single effective force determined by pair structure incurs major errors for describing processes associated with thermally activatedmore » escape from transiently localized states.« less

Authors:
ORCiD logo [1];  [1]
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  1. Univ. of Illinois at Urbana-Champaign, IL (United States)
Publication Date:
Research Org.:
Univ. of Illinois at Urbana-Champaign, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1634192
Grant/Contract Number:  
FG02-07ER46471
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review E
Additional Journal Information:
Journal Volume: 101; Journal Issue: 6; Journal ID: ISSN 2470-0045
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; colloidal glass; glassy systems; hard sphere colloids

Citation Formats

Ghosh, Ashesh, and Schweizer, Kenneth S. Microscopic theory of onset of decaging and bond-breaking activated dynamics in ultradense fluids with strong short-range attractions. United States: N. p., 2020. Web. doi:10.1103/PhysRevE.101.060601.
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Ghosh, Ashesh, & Schweizer, Kenneth S. Microscopic theory of onset of decaging and bond-breaking activated dynamics in ultradense fluids with strong short-range attractions. United States. https://doi.org/10.1103/PhysRevE.101.060601
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Ghosh, Ashesh, and Schweizer, Kenneth S. Fri . "Microscopic theory of onset of decaging and bond-breaking activated dynamics in ultradense fluids with strong short-range attractions". United States. https://doi.org/10.1103/PhysRevE.101.060601. https://www.osti.gov/servlets/purl/1634192.
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@article{osti_1634192,
title = {Microscopic theory of onset of decaging and bond-breaking activated dynamics in ultradense fluids with strong short-range attractions},
author = {Ghosh, Ashesh and Schweizer, Kenneth S.},
abstractNote = {We theoretically study thermally activated “in cage” elementary dynamical processes that precede full structural relaxation in ultra-dense particle liquids interacting via strong short range attractive forces. The analysis is based on a microscopic theory formulated at the particle trajectory level built on the dynamic free energy concept and an explicit treatment of how attractive forces control the formation and lifetime of physical bonds. Mean time scales for bond breaking, the early stage of cage escape, and non-Fickian displacement by a fixed amount are analyzed in the repulsive glass, bonded repulsive (attractive) glass, fluid, and dense gel regimes. The theory predicts a strong length-scale-dependent growth of these time scales with attractive force strength at fixed packing fraction, a much weaker slowing down with density at fixed attraction strength, and a strong decoupling of the shorter bond breaking time with the other two time scales that are controlled mainly by perturbed steric caging. All results are in good accord with simulations, and additional testable predictions are made. In conclusion, the classic statistical mechanical projection approximation of replacing all bare attractive and repulsive forces with a single effective force determined by pair structure incurs major errors for describing processes associated with thermally activated escape from transiently localized states.},
doi = {10.1103/PhysRevE.101.060601},
journal = {Physical Review E},
number = 6,
volume = 101,
place = {United States},
year = {Fri Jun 19 00:00:00 EDT 2020},
month = {Fri Jun 19 00:00:00 EDT 2020}
}
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https://doi.org/10.1103/PhysRevE.101.060601
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