Matyushov Dmitry V
Department of Physics and Department of Chemistry and Biochemistry, Arizona State University, PO Box 871504, Tempe, Arizona 85287-1504, USA.
J Chem Phys. 2014 Jun 14;140(22):224506. doi: 10.1063/1.4882284.
The standard Maxwell formulation of the problem of polarized dielectrics suffers from a number of difficulties, both conceptual and practical. These difficulties are particularly significant for liquid interfaces. For these systems, the ability of interfacial multipoles to change their orientations leads to the interfacial polarization localized within a thin microscopic layer. A formalism to capture this physical reality is proposed and is based on the surface charge as the source of microscopic electric fields in dielectrics. The surface charge density incorporates the local structure of the interface into electrostatic calculations. The corresponding surface susceptibility and interface dielectric constant provide local closures to the electrostatic boundary value problem. A robust approach to calculate the surface susceptibility from numerical simulations is formulated. The susceptibility can alternatively be extracted from a number of solution experiments, in particular those sensitive to the overall dipole moment of a closed dielectric surface. The theory is applied to the solvent-induced spectral shift and high-frequency dielectric response of solutions.
极化电介质问题的标准麦克斯韦公式存在许多概念和实际方面的困难。这些困难在液体界面的情况下尤为显著。对于这些系统，界面多极子改变其取向的能力导致界面极化局限于一个薄的微观层内。本文提出了一种形式体系来描述这一物理现实，该形式体系以表面电荷作为电介质中微观电场的源。表面电荷密度将界面的局部结构纳入静电计算中。相应的表面极化率和界面介电常数为静电边值问题提供了局部封闭条件。本文还制定了一种从数值模拟计算表面极化率的稳健方法。极化率也可以从一些溶液实验中提取，特别是那些对封闭介电表面的总偶极矩敏感的实验。该理论应用于溶液的溶剂诱导光谱位移和高频介电响应。
