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重新审视液体到理想玻璃态转变的复制品理论。

Revisiting the replica theory of the liquid to ideal glass transition.

作者信息

Bomont Jean-Marc, Hansen Jean-Pierre, Pastore Giorgio

机构信息

Université de Lorraine, LCP-A2MC, EA 3469, 1 Blvd. François Arago, Metz F-57078, France.

Université Pierre et Marie Curie, UMR 8234 PHENIX, Paris, France and Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, United Kingdom.

出版信息

J Chem Phys. 2019 Apr 21;150(15):154504. doi: 10.1063/1.5088811.

Abstract

The replica theory of the "Random First Order Transition" (RFOT) from a supercooled liquid to an "ideal" glass of a system of "soft spheres" is revisited. Following the seminal work of Mézard and Parisi [J. Chem. Phys. 111, 1076 (1999)], the number m of weakly interacting replicas of the system is varied continuously from m = 2 to m < 1. Relevant order parameters and the free energy of the liquid and glass phases are calculated using the hypernetted chain (HNC) approximation for the pair correlation functions. The scenario observed for all m confirms the existence of two glass branches G and G. The latter has the lowest free energy for all m > 1, while the former has a lower free energy for m < 1 but is shown to be unstable against spinodal decomposition for any nonzero value of the attractive inter-replica coupling. The critical temperature T of the RFOT turns out to depend on m, which may be a by-product of the approximation inherent in the HNC closure. The RFOT is predicted to be weakly first order, characterized by a small jump in density between the coexisting liquid and G phases for all m > 1. Estimating T in the limit m → 1 requires a proper extrapolation of high resolution HNC calculations. The present protocol explores the behavior of the free energy of the ideal glass phase below T as a function of m.

摘要

重新审视了“随机一级转变”(RFOT)的复本理论,该理论描述了过冷液体到“软球”系统的“理想”玻璃态的转变。继梅扎德(Mézard)和帕里西(Parisi)的开创性工作[《化学物理杂志》111, 1076 (1999)]之后,系统中弱相互作用复本的数量m从m = 2连续变化到m < 1。使用对关联函数的超网链(HNC)近似计算了液相和玻璃相的相关序参量和自由能。对于所有m观察到的情况证实了存在两个玻璃分支G和G。对于所有m > 1,后者具有最低的自由能,而对于m < 1,前者具有较低的自由能,但对于任何非零的吸引性复本间耦合值,它对旋节线分解是不稳定的。结果表明,RFOT的临界温度T取决于m,这可能是HNC封闭中固有近似的一个副产品。预计RFOT是弱一级的,其特征是对于所有m > 1,共存液相和G相之间的密度有小的跳跃。在m → 1的极限下估计T需要对高分辨率HNC计算进行适当的外推。本文方案探讨了低于T时理想玻璃相自由能随m的变化行为。

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