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具有竞争相互作用的液体非平衡态非晶凝固。

Non-equilibrium view of the amorphous solidification of liquids with competing interactions.

机构信息

Instituto de Física "Manuel Sandoval Vallarta," Universidad Autónoma de San Luis Potosí, Álvaro Obregón 64, 78000 San Luis Potosí, Mexico.

Instituto de Física, Benemérita Universidad Autónoma de Puebla, Apartado Postal J-48 72570, Puebla, Mexico.

出版信息

J Chem Phys. 2023 Feb 14;158(6):064506. doi: 10.1063/5.0132525.

Abstract

The interplay between short-range attractions and long-range repulsions (SALR) characterizes the so-called liquids with competing interactions, which are known to exhibit a variety of equilibrium and non-equilibrium phases. The theoretical description of the phenomenology associated with glassy or gel states in these systems has to take into account both the presence of thermodynamic instabilities (such as those defining the spinodal line and the so called λ line) and the limited capability to describe genuine non-equilibrium processes from first principles. Here, we report the first application of the non-equilibrium self-consistent generalized Langevin equation theory to the description of the dynamical arrest processes that occur in SALR systems after being instantaneously quenched into a state point in the regions of thermodynamic instability. The physical scenario predicted by this theory reveals an amazing interplay between the thermodynamically driven instabilities, favoring equilibrium macro- and micro-phase separation, and the kinetic arrest mechanisms, favoring non-equilibrium amorphous solidification of the liquid into an unexpected variety of glass and gel states.

摘要

短程吸引力和长程斥力(SALR)的相互作用特征化了所谓的具有竞争相互作用的液体,这些液体已知表现出多种平衡和非平衡相。在这些系统中,与玻璃态或凝胶态相关的现象学的理论描述必须考虑到热力学不稳定性的存在(例如那些定义了旋度线和所谓的 λ 线的不稳定性)以及从第一性原理描述真正非平衡过程的有限能力。在这里,我们首次将非平衡自洽广义朗之万方程理论应用于 SALR 系统在瞬间被淬火到热力学不稳定区域中的状态点后发生的动力学捕获过程的描述。该理论预测的物理情景揭示了热力学驱动的不稳定性和动力学捕获机制之间的惊人相互作用,前者有利于平衡宏观和微观相分离,后者有利于液体非平衡无定形固化为各种出乎意料的玻璃和凝胶态。

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