TY - JOUR
T1 - Limitations of heterogeneous models of liquid dynamics
T2 - Very slow rate exchange in the excess wing
AU - Samanta, Subarna
AU - Richert, Ranko
PY - 2014/2/7
Y1 - 2014/2/7
N2 - For several molecular glass formers, the nonlinear dielectric effects (NDE's) are investigated for the so-called excess wing regime, i.e., for the relatively high frequencies between 102 and 107 times the peak loss frequency. It is found that significant nonlinear behavior persists across the entire frequency window of this study, and that its magnitude traces the temperature dependence of the activation energy. A time resolved measurement of the dielectric loss at fields up to 480 kV/cm across tens of thousands of periods reveals that it takes an unexpectedly long time for the steady state NDE to develop. For various materials and at different temperatures and frequencies, it is found that the average structural relaxation with time scale τα governs the equilibration of these fast modes that are associated with time constants τ which are up to 107 times shorter than τα. It is argued that true indicators of structural relaxation (such as rate exchange and aging) of these fast modes are slaved to macroscopic softening on the time scale of τα, and thus many orders of magnitude slower than the time constant of the mode itself.
AB - For several molecular glass formers, the nonlinear dielectric effects (NDE's) are investigated for the so-called excess wing regime, i.e., for the relatively high frequencies between 102 and 107 times the peak loss frequency. It is found that significant nonlinear behavior persists across the entire frequency window of this study, and that its magnitude traces the temperature dependence of the activation energy. A time resolved measurement of the dielectric loss at fields up to 480 kV/cm across tens of thousands of periods reveals that it takes an unexpectedly long time for the steady state NDE to develop. For various materials and at different temperatures and frequencies, it is found that the average structural relaxation with time scale τα governs the equilibration of these fast modes that are associated with time constants τ which are up to 107 times shorter than τα. It is argued that true indicators of structural relaxation (such as rate exchange and aging) of these fast modes are slaved to macroscopic softening on the time scale of τα, and thus many orders of magnitude slower than the time constant of the mode itself.
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U2 - 10.1063/1.4863347
DO - 10.1063/1.4863347
M3 - Article
AN - SCOPUS:84903745728
SN - 0021-9606
VL - 140
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 5
M1 - 054503
ER -