TY - JOUR
T1 - Relationships between the single particle barrier hopping theory and thermodynamic, disordered media, elastic, and jamming models of glassy systems
AU - Schweizer, Kenneth S.
N1 - This work was supported by the National Science Foundation via the Nanoscience and Engineering Center for the Directed Assembly of Nanostructures via Grant No. DMR-0642573. The author acknowledge helpful and informative correspondence with Jeppe Dyre on elastic models, Jack Douglas on entropy theories and normal state dynamics, Sal Torquato on jamming, and Peter Wolynes on the random first order phase transition theory of glasses. Comments on the manuscript by J. Dyre, D. Reichman, and G. Szamel are gratefully acknowledged.
PY - 2007
Y1 - 2007
N2 - The predictions of the ultralocal limit of the activated hopping theory of highly viscous simple fluids and colloidal suspensions [K. S. Schweizer and G. Yatsenko, J. Chem. Phys. 127, 164505 (2007), preceding paper] for the relaxation time and effective activation barrier are compared with those of diverse alternative theoretical approaches and computer simulation. A nonlinear connection between the barrier height and excess pressure as empirically suggested by simulations of polydisperse repulsive force fluids is identified. In the dense normal and weakly dynamical precursor regime, where entropic barriers of hard spheres are nonexistent or of order the thermal energy, agreement with an excess entropy ansatz is found. In the random close packing or jamming limit, the barrier hopping theory predicts an essential singularity stronger than the free volume model, which is in agreement with the simplest entropic droplet nucleation and replica field theoretic approaches. Upon further technical simplification of the theory, close connections with renormalization group and nonperturbative memory function based studies of activated transport of a Brownian particle in a disordered medium, can been identified. Several analytic arguments suggest a qualitative consistency between the barrier hopping theory and solid-state elastic models based on the high frequency shear modulus and a molecular-sized apparent activation volume. Implications of the analysis for the often high degeneracy of conflicting explanations of glassy dynamics are discussed.
AB - The predictions of the ultralocal limit of the activated hopping theory of highly viscous simple fluids and colloidal suspensions [K. S. Schweizer and G. Yatsenko, J. Chem. Phys. 127, 164505 (2007), preceding paper] for the relaxation time and effective activation barrier are compared with those of diverse alternative theoretical approaches and computer simulation. A nonlinear connection between the barrier height and excess pressure as empirically suggested by simulations of polydisperse repulsive force fluids is identified. In the dense normal and weakly dynamical precursor regime, where entropic barriers of hard spheres are nonexistent or of order the thermal energy, agreement with an excess entropy ansatz is found. In the random close packing or jamming limit, the barrier hopping theory predicts an essential singularity stronger than the free volume model, which is in agreement with the simplest entropic droplet nucleation and replica field theoretic approaches. Upon further technical simplification of the theory, close connections with renormalization group and nonperturbative memory function based studies of activated transport of a Brownian particle in a disordered medium, can been identified. Several analytic arguments suggest a qualitative consistency between the barrier hopping theory and solid-state elastic models based on the high frequency shear modulus and a molecular-sized apparent activation volume. Implications of the analysis for the often high degeneracy of conflicting explanations of glassy dynamics are discussed.
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U2 - 10.1063/1.2780863
DO - 10.1063/1.2780863
M3 - Article
C2 - 17979359
AN - SCOPUS:36049041600
SN - 0021-9606
VL - 127
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 16
M1 - 164506
ER -