Schweizer Kenneth S
Department of Materials Science, University of Illinois, Urbana, Illinois 61801, USA.
J Chem Phys. 2007 Oct 28;127(16):164506. doi: 10.1063/1.2780863.
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.
将高粘性简单流体和胶体悬浮液的活化跳跃理论[K. S. 施韦泽和G. 亚采年科,《化学物理杂志》127, 164505 (2007),前文]的超局部极限对弛豫时间和有效活化势垒的预测,与各种不同的替代理论方法和计算机模拟的预测进行了比较。确定了多分散排斥力流体模拟经验性建议的势垒高度与过剩压力之间的非线性联系。在致密正常和弱动力学前驱体区域,硬球的熵垒不存在或为热能量级,发现与过剩熵假设相符。在随机密堆积或堵塞极限下,势垒跳跃理论预测的本质奇点比自由体积模型更强,这与最简单的熵滴核化和复制场论方法一致。在对该理论进行进一步技术简化后,可以确定与基于重整化群和非微扰记忆函数的无序介质中布朗粒子活化输运研究的紧密联系。几个分析论证表明势垒跳跃理论与基于高频剪切模量和分子尺寸表观活化体积的固态弹性模型之间存在定性一致性。讨论了该分析对玻璃态动力学中经常出现的相互冲突解释的高度简并性的影响。