The dynamics of chemical reactions in liquid solutions are now amenable to direct study using ultrafast laser spectroscopy techniques and advances in computer simulation methods. The surrounding solvent affects the chemical reaction dynamics in numerous ways, which include: (i) formation of complexes between reactants and solvent molecules; (ii) modifications to transition state energies and structures relative to the reactants and products; (iii) coupling between the motions of the reacting molecules and the solvent modes, and exchange of energy; (iv) solvent caging of reactants and products; and (v) structural changes to the solvation shells in response to the changing chemical identity of the solutes, on timescales which may be slower than the reactive events. This article reviews progress in the study of bimolecular chemical reaction dynamics in solution, concentrating on reactions which occur on ground electronic states. It illustrates this progress with reference to recent experimental and computational studies, and considers how the various ways in which a solvent affects the chemical reaction dynamics can be unravelled. Implications are considered for research in fields such as mechanistic synthetic chemistry.

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冒险：液体中的化学反应动力学

液体溶液中化学反应的动力学现在可以使用超快激光光谱技术直接研究，并且可以在计算机模拟方法中取得进步。周围的溶剂以多种方式影响化学反应动力学，包括：（i）反应物和溶剂分子之间形成络合物；（ii）改变相对于反应物和产物的过渡态能量和结构；（iii）反应分子的运动与溶剂模式之间的耦合，以及能量的交换；（iv）反应物和产物的溶剂笼养；（v）响应于溶质化学特性的变化，溶剂化壳的结构发生了变化，变化的时间尺度可能比反应性事件慢。本文概述了溶液中双分子化学反应动力学的研究进展，重点是在基态电子状态下发生的反应。它参考最近的实验和计算研究说明了这一进展，并考虑了如何阐明溶剂影响化学反应动力学的各种方式。在机械合成化学等领域的研究中考虑了其含义。