Helfferich Julian
Theoretical Polymer Physics, University of Freiburg, Hermann-Herder-Str. 3, 79104, Freiburg, Germany,
Eur Phys J E Soft Matter. 2014 Aug;37(8):32. doi: 10.1140/epje/i2014-14073-6. Epub 2014 Aug 27.
On cooling toward the glass transition temperature, glass-forming liquids display long periods of localized motion interrupted by fast "jumps" in the single-particle trajectories. Several theoretical models based on these single-particle jumps have been proposed, most prominently the continuous-time random walk (CTRW). The central assumption of the CTRW is that jumps are renewal events, i.e. that the internal clock of a particle can be reset upon a jump. In this paper, I present an easy-to-implement method to test whether jumps detected in a supercooled liquid or glass are renewal events or not. The test was applied to molecular dynamics simulations of a short-chain polymer melt, demonstrating that the jumps can in fact be treated as renewal events. The test further revealed that additional relaxation processes are present which are not accounted for in the CTRW picture, highlighting the limitations of this approach. The notion of renewal events in glass-forming systems could be a very important building block for the interpretation of aging and the glass transition. Furthermore, it could have practical implications for the study of non-equilibrium dynamics in glasses as well as mechanical rejuvenation.
在朝着玻璃化转变温度冷却时,玻璃形成液体表现出长时间的局部运动,这种运动被单粒子轨迹中的快速“跳跃”打断。基于这些单粒子跳跃,已经提出了几种理论模型,其中最著名的是连续时间随机游走(CTRW)。CTRW的核心假设是跳跃是更新事件,即粒子的内部时钟在跳跃时可以重置。在本文中,我提出了一种易于实现的方法,用于测试在过冷液体或玻璃中检测到的跳跃是否为更新事件。该测试应用于短链聚合物熔体的分子动力学模拟,表明这些跳跃实际上可以被视为更新事件。该测试还进一步揭示,存在额外的弛豫过程,而CTRW模型并未考虑这些过程,这突出了该方法的局限性。玻璃形成系统中的更新事件概念可能是解释老化和玻璃化转变的一个非常重要的组成部分。此外,它可能对玻璃中非平衡动力学的研究以及机械恢复活力具有实际意义。