TY - JOUR

T1 - Thermodynamics-Structure-Dynamics Correlations and Nonuniversal Effects in the Elastically Collective Activated Hopping Theory of Glass-Forming Liquids

AU - Mei, Baicheng

AU - Zhou, Yuxing

AU - Schweizer, Kenneth S.

N1 - Funding Information:
Y.Z. and K.S.S. acknowledge support from the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division. B.M. and K.S.S. acknowledge support from DOE-BES under Grant DE-FG02-07ER46471 administered through the Materials Research Laboratory at UIUC.
Publisher Copyright:
Copyright © 2020 American Chemical Society.

PY - 2020/7/16

Y1 - 2020/7/16

N2 - We employ the microscopic Elastically Collective Nonlinear Langevin Equation (ECNLE) theory of activated dynamics in combination with crystal-avoiding simulations to study four inter-related questions for metastable monodisperse hard sphere fluids. The first is how significantly improved integral equation theory structural input (Modified-Verlet (MV) closure) changes the dynamical predictions of ECNLE theory. The main consequence is a modest enhancement of the importance of the collective elastic barrier relative to its local cage contribution, which increases the alpha relaxation time and fragility relative to prior results based on the Percus-Yevick closure. Second, ECNLE-MV theory predictions for the alpha time and self-diffusion constant in the metastable regime are quantitatively compared to our new simulations. The small adjustment of a numerical prefactor that enters the collective elastic barrier leads to quantitative agreement over three decades. Third, using the more accurate MV structural input, ECNLE theory is shown to predict thermodynamics-structure-dynamics "correlations"based on various long and short wavelength scalar properties all related to static two-point collective density fluctuations. The logarithm of the alpha relaxation time scales as a power law with these scalar metrics with an exponent that is significantly lower in the less dense noncooperative activated regime compared to the very dense highly cooperative regime. However, the discovered correlation of activated relaxation with a thermodynamic property (dimensionless compressibility) is not causal in ECNLE theory, but rather reflects a strong connection between the local structural quantities that quantify kinetic constraints in the theory with the amplitude of long wavelength density fluctuations. Fourth, the consequences of chemically specific nonuniversalities associated with the onset condition and relative importance of collective elasticity are studied. The predicted thermodynamics-structure-dynamics correlations are found to be robust, albeit with nontrivial shifts of the onset condition.

AB - We employ the microscopic Elastically Collective Nonlinear Langevin Equation (ECNLE) theory of activated dynamics in combination with crystal-avoiding simulations to study four inter-related questions for metastable monodisperse hard sphere fluids. The first is how significantly improved integral equation theory structural input (Modified-Verlet (MV) closure) changes the dynamical predictions of ECNLE theory. The main consequence is a modest enhancement of the importance of the collective elastic barrier relative to its local cage contribution, which increases the alpha relaxation time and fragility relative to prior results based on the Percus-Yevick closure. Second, ECNLE-MV theory predictions for the alpha time and self-diffusion constant in the metastable regime are quantitatively compared to our new simulations. The small adjustment of a numerical prefactor that enters the collective elastic barrier leads to quantitative agreement over three decades. Third, using the more accurate MV structural input, ECNLE theory is shown to predict thermodynamics-structure-dynamics "correlations"based on various long and short wavelength scalar properties all related to static two-point collective density fluctuations. The logarithm of the alpha relaxation time scales as a power law with these scalar metrics with an exponent that is significantly lower in the less dense noncooperative activated regime compared to the very dense highly cooperative regime. However, the discovered correlation of activated relaxation with a thermodynamic property (dimensionless compressibility) is not causal in ECNLE theory, but rather reflects a strong connection between the local structural quantities that quantify kinetic constraints in the theory with the amplitude of long wavelength density fluctuations. Fourth, the consequences of chemically specific nonuniversalities associated with the onset condition and relative importance of collective elasticity are studied. The predicted thermodynamics-structure-dynamics correlations are found to be robust, albeit with nontrivial shifts of the onset condition.

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U2 - 10.1021/acs.jpcb.0c03613

DO - 10.1021/acs.jpcb.0c03613

M3 - Article

C2 - 32633526

AN - SCOPUS:85088244399

SN - 1520-6106

VL - 124

SP - 6121

EP - 6131

JO - Journal of Physical Chemistry B

JF - Journal of Physical Chemistry B

IS - 28

ER -