Bomont Jean-Marc, Pastore Giorgio, Costa Dino, Munaò Gianmarco, Malescio Gianpietro, Prestipino Santi
Université de Lorraine, LCP-A2MC, UR 3469, 1 Bd. François Arago, Metz F-57078, France.
Dipartimento di Fisica, Università degli Studi di Trieste, Strada Costiera 11, 34151 Grignano (Trieste), Italy.
J Chem Phys. 2024 Jun 7;160(21). doi: 10.1063/5.0208117.
We present the first systematic application of the integral equation implementation of the replica method to the study of arrested states in fluids with microscopic competing interactions (short-range attractive and long-range repulsive, SALR), as exemplified by the prototype Lennard-Jones-Yukawa model. Using a wide set of potential parameters, we provide as many as 11 different phase diagrams on the density (ρ)-temperature (T) plane, embodying both the cluster-phase boundary, TC(ρ), and the locus below which arrest takes place, TD(ρ). We describe how the interplay between TC and TD-with the former falling on top of the other, or the other way around, depending on thermodynamic conditions and potential parameters-gives rise to a rich variety of non-ergodic states interspersed with ergodic ones, of which both the building blocks are clusters or single particles. In a few cases, we find that the TD locus does not extend all over the density range subtended by the TC envelope; under these conditions, the λ-line is within reach of the cluster fluid, with the ensuing possibility to develop ordered microphases. Whenever a comparison is possible, our predictions favorably agree with previous numerical results. Thereby, we demonstrate the reliability and effectiveness of our scheme to provide a unified theoretical framework for the study of arrested states in SALR fluids, irrespective of their nature.
我们首次将复制品方法的积分方程实现系统地应用于研究具有微观竞争相互作用（短程吸引和长程排斥，SALR）的流体中的非平衡态，以原型 Lennard-Jones-Yukawa 模型为例。通过使用广泛的势参数集，我们在密度（ρ）-温度（T）平面上提供了多达 11 种不同的相图，体现了团簇相边界 TC(ρ) 以及发生非平衡态的下限轨迹 TD(ρ)。我们描述了 TC 和 TD 之间的相互作用——前者落在后者之上，或者反之，这取决于热力学条件和势参数——如何产生丰富多样的非遍历态，这些非遍历态穿插着遍历态，其基本组成部分都是团簇或单个粒子。在少数情况下，我们发现 TD 轨迹并不延伸到 TC 包络所涵盖的整个密度范围；在这些条件下，λ 线处于团簇流体的范围内，随之有可能形成有序微相。只要有可能进行比较，我们的预测就与先前的数值结果吻合良好。由此，我们证明了我们的方案为研究 SALR 流体中的非平衡态提供统一理论框架的可靠性和有效性，无论其性质如何。
