Solvent Cage Effects and the Dynamics of Liquid State Chemical Reactions

在这个理论与计算化学的项目中， 物理化学计划的子计划，阿德尔曼将 研究三个基本过程的动力学，振动 能量弛豫、光解笼逃逸和活化 在液态下普遍存在的势垒穿越 化学. 拟议研究的目标有四个方面： (i)为了更好地理解溶质运动， 这些基本过程的基础;（二）导出 振动能等观测量的解析公式 弛豫时间和非成对量子产率， 透明地反映溶质的定性性质 （三）制定实用的半定量 选择分子溶质摩擦核的公式; （iv）发展简化的随机动力学模拟 模拟溶质运动的方法。 这项工作应该提供新的基本认识， 液态反应动力学 它还应该提供 实验解释的定量框架 数据 最后，它应该提供计算工具， 应用将导致知识的进一步增长。

In this project in the Theoretical and Computational Chemistry Subprogram of the Physical Chemistry Program, Adelman will study the dynamics of three elementary processes, vibrational energy relaxation, photolytic cage escape, and activated barrier crossing, which occur ubiquitously in liquid state chemistry. The goals of the proposed research are four-fold: (i) To obtain an improved understanding of the solute motions which underlie these elementary processes; (ii) To derive analytical formulas for observables like the vibrational energy relaxation time and the non-geminate quantum yield which transparently reflect the qualitative nature of the solute motions; (iii) To develop practical semi-quantitative prescriptions for choosing molecular solute friction kernels; and (iv) To develop simplified stochastic dynamics simulation methods for simulating the solute motions. This work should provide new fundamental understanding of liquid state reaction dynamics. It also should provide quantitative frameworks for the interpretation of experimental data. And lastly it should provide computational tools whose application will lead to further increases in knowledge.