任意维度下的 Stokes-Einstein 关系的微观模型。

A microscopic model of the Stokes-Einstein relation in arbitrary dimension.

机构信息

Department of Pure Mathematics, University of Waterloo, Waterloo, Ontario N2L 3G3, Canada.

Department of Chemistry, Duke University, Durham, North Carolina 27708, USA.

出版信息

J Chem Phys. 2018 Jun 14;148(22):224503. doi: 10.1063/1.5029464.

DOI:10.1063/1.5029464

PMID:29907017

Abstract

The Stokes-Einstein relation (SER) is one of the most robust and widely employed results from the theory of liquids. Yet sizable deviations can be observed for self-solvation, which cannot be explained by the standard hydrodynamic derivation. Here, we revisit the work of Masters and Madden [J. Chem. Phys. 74, 2450-2459 (1981)], who first solved a statistical mechanics model of the SER using the projection operator formalism. By generalizing their analysis to all spatial dimensions and to partially structured solvents, we identify a potential microscopic origin of some of these deviations. We also reproduce the SER-like result from the exact dynamics of infinite-dimensional fluids.

摘要

斯托克斯-爱因斯坦关系（SER）是液体理论中最可靠和应用最广泛的结果之一。然而，对于自溶剂化，我们可以观察到相当大的偏差，这不能用标准的流体力学推导来解释。在这里，我们重新审视了马斯特斯和马登（Masters and Madden）的工作[J. Chem. Phys. 74, 2450-2459 (1981)]，他们首次使用投影算子形式主义解决了 SER 的统计力学模型。通过将他们的分析推广到所有空间维度和部分结构溶剂，我们确定了这些偏差的一些潜在微观起源。我们还从无限维流体的精确动力学中重现了类似 SER 的结果。