论文标题
动态疏水溶剂壳形成的光谱特征
Spectroscopic Signatures of the Dynamical Hydrophobic Solvation Shell Formation
论文作者
论文摘要
当水中的亲水性溶质突然变成疏水物种时,例如,通过光电离,一层水合水分子在溶质周围以几个picseconds的时间尺度形成。我们根据时间依赖性的电介质连续体模型研究了在疏水溶质周围的水合壳的动态积聚。有关溶剂的信息是从光谱中从非平衡溶剂中的静态Onsager球体内的测试偶极子的弛豫动力学中提取的。生长过程在两种方法中被现象学描述。首先,我们考虑了水合层的时间相关厚度,该层在有限的时间内从零生长到有限值。其次,我们假设围绕Onsager球体的有限层区域内的时间依赖性复杂介电常数。该层被建模为连续介电动力学较慢的连续介电。我们发现与散装水相比,我们发现偶极子的蓝色转移到偶极子的共振吸收的蓝色,并动态降低线宽度。蓝移反映了针对整体溶剂的氢键网络所做的工作,并且是可直接测量的数量。我们的结果与水中碘疏水溶剂化的实验一致。
When a hydrophilic solute in water is suddenly turned into a hydrophobic species, for instance, by photoionization, a layer of hydrated water molecules forms around the solute on a time scale of a few picoseconds. We study the dynamic build-up of the hydration shell around a hydrophobic solute on the basis of a time-dependent dielectric continuum model. Information about the solvent is spectroscopically extracted from the relaxation dynamics of a test dipole inside a static Onsager sphere in the nonequilibrium solvent. The growth process is described phenomenologically within two approaches. First, we consider a time-dependent thickness of the hydration layer which grows from zero to a finite value over a finite time. Second, we assume a time-dependent complex permittivity within a finite layer region around the Onsager sphere. The layer is modeled as a continuous dielectric with a much slower fluctuation dynamics. We find a time-dependent frequency shift down to the blue of the resonant absorption of the dipole, together with a dynamically decreasing line width, as compared to bulk water. The blue shift reflects the work performed against the hydrogen bonded network of the bulk solvent and is a directly measurable quantity. Our results are in agreement with an experiment on the hydrophobic solvation of iodine in water.