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溶剂不均匀性在决定纳米聚集体之间色散相互作用中的作用。

The role of solvent heterogeneity in determining the dispersion interaction between nanoassemblies.

作者信息

Chun Jaehun, Mundy Christopher J, Schenter Gregory K

机构信息

†Nuclear Sciences Division and ‡Physical Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99354, United States.

出版信息

J Phys Chem B. 2015 May 7;119(18):5873-81. doi: 10.1021/jp512550c. Epub 2015 Apr 24.

Abstract

Understanding fundamental nanoassembly processes on intermediate scales between molecular and continuum scales requires an in-depth analysis of the coupling between particle interactions and molecular details. This is because the discrete nature of the solvent becomes comparable to the characteristic length scales of assembly. Utilizing the spatial density response of a solvent to a surface in conjunction with the Clausius-Mossotti equation, we present a simple theory relating the discrete nature of solvent to dispersion interactions. Our study reveals that dispersion interactions are indeed sensitive to the spatial variation of solvent density, manifesting in dramatic deviations in van der Waals forces from the conventional formulation (e.g., with uniform solvent density). This study provides the first steps toward relating molecular scale principles, namely the detailed nature of solvent response to an interface, to the underlying hydration forces between surfaces.

摘要

理解分子尺度和连续介质尺度之间中间尺度上的基本纳米组装过程,需要深入分析粒子相互作用与分子细节之间的耦合。这是因为溶剂的离散性质变得与组装的特征长度尺度相当。结合溶剂对表面的空间密度响应和克劳修斯-莫索蒂方程,我们提出了一个将溶剂的离散性质与色散相互作用联系起来的简单理论。我们的研究表明,色散相互作用确实对溶剂密度的空间变化敏感,表现为范德华力与传统公式(例如,溶剂密度均匀时)有显著偏差。这项研究朝着将分子尺度原理,即溶剂对界面响应的详细性质,与表面之间潜在的水化力联系起来迈出了第一步。

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