重新审视瞬时正态模态告诉我们关于液体动力学的问题。

IF 3.1 2区 化学 Q3 CHEMISTRY, PHYSICAL
Sha Jin, Xue Fan, Matteo Baggioli
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引用次数: 0

摘要

长期以来,缺乏定义良好的平衡参考构型阻碍了对液体动力学和性质的全面的原子水平理解。瞬态正态模(INM)方法涉及对瞬时液体构型中势能的Hessian矩阵进行对角化,已成为这一方向上有前途的框架。然而,一些概念上的挑战仍然存在,特别是与该方法无法捕捉非谐波效应有关。在这项研究中,我们通过对模拟系统(包括Ar、Xe、N2、CS2、Ga和Pb)在从固相到气相的广泛温度范围内的综合INM分析,提出了一组“实验事实”。首先,我们检查INM状态密度(DOS),并将其与从速度自相关函数获得的DOS进行比较。然后,我们分析了不稳定模态的分数和INM DOS的低频斜率的温度依赖性,以寻找潜在的普遍行为。此外,我们还探讨了INMs与液体的其他性质之间的关系,包括类液到类气的动力学交叉和集体剪切波的动量间隙。此外,我们研究了系统接近固相时低温下的INM光谱,揭示了即使在结晶固体中也有很大一部分不稳定模式。最后,我们证实了INM特征值谱中最近讨论的尖点样奇点的存在,并揭示了其复杂的温度依赖行为,挑战了当前的理论模型。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Revisiting the question of what instantaneous normal modes tell us about liquid dynamics.

The lack of a well-defined equilibrium reference configuration has long hindered a comprehensive atomic-level understanding of liquid dynamics and properties. The Instantaneous Normal Mode (INM) approach, which involves diagonalizing the Hessian matrix of potential energy in instantaneous liquid configurations, has emerged as a promising framework in this direction. However, several conceptual challenges remain, particularly related to the approach's inability to capture anharmonic effects. In this study, we present a set of "experimental facts" through a comprehensive INM analysis of simulated systems, including Ar, Xe, N2, CS2, Ga, and Pb, across a wide temperature range from the solid to gas phase. First, we examine the INM density of states (DOS) and compare it to the DOS obtained from the velocity auto-correlation function. We then analyze the temperature dependence of the fraction of unstable modes and the low-frequency slope of the INM DOS in search of potential universal behaviors. Furthermore, we explore the relationship between INMs and other properties of liquids, including the liquid-like to gas-like dynamical crossover and the momentum gap of collective shear waves. In addition, we investigate the INM spectrum at low temperatures as the system approaches the solid phase, revealing a significant fraction of unstable modes even in crystalline solids. Finally, we confirm the existence of a recently discussed cusp-like singularity in the INM eigenvalue spectrum and uncover its complex temperature-dependent behavior, challenging current theoretical models.

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来源期刊
Journal of Chemical Physics
Journal of Chemical Physics 物理-物理:原子、分子和化学物理
CiteScore
7.40
自引率
15.90%
发文量
1615
审稿时长
2 months
期刊介绍: The Journal of Chemical Physics publishes quantitative and rigorous science of long-lasting value in methods and applications of chemical physics. The Journal also publishes brief Communications of significant new findings, Perspectives on the latest advances in the field, and Special Topic issues. The Journal focuses on innovative research in experimental and theoretical areas of chemical physics, including spectroscopy, dynamics, kinetics, statistical mechanics, and quantum mechanics. In addition, topical areas such as polymers, soft matter, materials, surfaces/interfaces, and systems of biological relevance are of increasing importance. Topical coverage includes: Theoretical Methods and Algorithms Advanced Experimental Techniques Atoms, Molecules, and Clusters Liquids, Glasses, and Crystals Surfaces, Interfaces, and Materials Polymers and Soft Matter Biological Molecules and Networks.
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