School of Molecular Sciences, Arizona State University, Tempe, AZ 85287, USA.
Phys Chem Chem Phys. 2018 Dec 19;21(1):32-37. doi: 10.1039/c8cp05161e.
We observe structural recovery after an electric field step by probing the dielectric loss profile near its maximum, which displays a field-induced shift towards lower frequencies. These dynamics display time aging-time superposition (TaTS) for the majority of relaxation modes, thus implying homogeneous recovery dynamics. Although assumed by generally accepted models, the same modes can not be responsible for structural relaxation and for structural recovery, as the former is heterogeneous and the latter is homogeneous regarding the nature of the dynamics. This conflict is resolved by proposing that structural recovery is governed by rate exchange, a process that refers to the homogeneous fluctuations of rate constants in equilibrium and restores ergodicity more slowly than the relaxation observed as a simple correlation decay. This recognition has wide-ranging consequences on how aging and nonlinear dynamics such as scanning calorimetry should be modeled.
我们通过探测介电损耗谱在最大值附近的变化来观察电场阶跃后的结构恢复,介电损耗谱显示出向低频移动的场致位移。这些动力学在大多数弛豫模式中表现出时老化-时间叠加(TaTS),因此暗示了均匀的恢复动力学。尽管被普遍接受的模型所假设,但相同的模式不能同时负责结构弛豫和结构恢复,因为前者是异质的,而后者在动力学的性质上是均匀的。通过提出结构恢复由速率交换控制,可以解决这一冲突,速率交换是指在平衡时速率常数的均匀波动,并且比作为简单相关衰减观察到的弛豫恢复遍历性更慢。这种认识对老化和非线性动力学(如扫描量热法)的建模方式具有广泛的影响。