论文标题
时间依赖性的Stokes移位对非平衡结构溶解动力学的时间分辨探测
Time-Resolved Probing of the Nonequilibrium Structural Solvation Dynamics by the Time-Dependent Stokes Shift
论文作者
论文摘要
时间依赖性的荧光变速者可以监测光激发溶质分子周围的极性溶剂的极化的松弛，还可以在光激发后溶质的结构变化和随后的分子电荷重新分布。在这里，我们为明确的时间依赖性连续溶剂制定了简单的非平衡量子溶剂化理论。时间依赖性溶剂会诱导溶剂动力学上的非平衡波动，这些动力学直接反映在时间依赖性的Stokes移动中的不同时间成分中。我们通过动态缩小的溶质的示例来说明存在明显时间依赖的溶剂的结构动力学，从而导致双模式的stokes变化。有趣的是，这两种贡献都是相互耦合的。此外，我们可以解释与缓慢的结构动力学变化相关的Stokes转移的突出的长尾衰减。
The time-dependent fluorescence Stokes shifts monitors the relaxation of the polarization of a polar solvent in the surroundings of a photoexcited solute molecule, but also the structural variation of the solute following photoexcitation and the subsequent molecular charge redistribution. Here, we formulate a simple nonequilibrium quantum theory of solvation for an explicitly time-dependent continuous solvent. The time-dependent solvent induces nonequilibrium fluctuations on the solvent dynamics which are directly reflected in different time components in the time-dependent Stokes shift. We illustrate the structural dynamics in the presence of an explicitly time-dependent solvent by the example of a dynamically shrinking solute which leads to a bi-modal Stokes shift. Interestingly, both contributions are mutually coupled. Furthermore, we can explain a prominent long-tail decay of the Stokes shift associated to slow structural dynamical variations.
