Nonadiabatic Molecular Dynamics in Condensed Systems

大卫科克得到了理论和 计算化学计划，以继续他的研究在非绝热 凝聚系统中的分子动力学 Coker正在合并 非绝热开关形式主义与表面跳跃理论研究 量子子系统和经典子系统之间的能量再分配。 这 导致了一种新的方法来处理非绝热动力学， 凝聚相系统 将开发更多的新方法， 模拟系统与几个非绝热量子自由度， 存在一个经典的浴自由度。 的应用 探索核非绝热性包括：1）研究 溶剂密度对氢非绝热转动动力学的影响 分子在溶液中的转动行为及其对转动拉曼光谱的影响 线宽; 2）非绝热动力学和隧道效应对 氢分子在冰中的输运; 3）溶液相的研究 分子间质子转移反应及溶剂效应 极化和平面性对质子隧穿和非绝热性的影响 动力学 溶液相反应中的电子非绝热性将是 通过引入半经验价键方法进行研究 在分子中被称为“化学”。 这种方法将用于早期研究 双原子碘光激发后的时间非绝热动力学， 双原子碘阴离子和碘甲烷在各种分子溶剂中的溶液。 由于大多数工业合成过程发生在溶液中， 重要的是要更多地了解影响， 溶剂对溶剂化体系中基本化学过程的影响 包括分子运输、质子转移和电子 激发 这一理论研究将导致改进的 了解影响化学反应的因素， 溶液

David Coker is supported by a grant from the Theoretical and Computational Chemistry Program to continue his research in nonadiabatic molecular dynamics in condensed systems. Coker is combining nonadiabatic switching formalism with surface hopping theory to study energy redistribution between quantum and classical subsystems. This has resulted in a new approach for treating nonadiabatic dynamics in condensed phase systems. Additional new methods will be developed for simulating systems with few nonadiabatic quantum degrees of freedom in the presence of a classical bath degrees of freedom. Applications which explore nuclear nonadiabaticity include: 1) studies of the effects of solvent density on the nonadiabatic rotational dynamics of hydrogen molecule in solution and the influence they have on rotational Raman linewidths; 2) the influence of nonadiabatic dynamics and tunneling on transport of hydrogen molecule in ice; and 3) studies of solution phase intermolecular proton transfer reactions and the effects of solvent polarization and planarity on tunneling and nonadiabaticity of proton dynamics. Electronic nonadiabaticity in solution phase reactions will be studied by the introduction of a semi-empirical valence bond approach called diatomics in molecules. This approach will be used to study early time nonadiabatic dynamics after photoexcitation of diatomic iodine, diatomic iodine anion, and methyl iodide in various molecular solvents. Since most industrial synthetic processes occur in solution, it is important to gain an increased understanding of the influence which solvent has on fundamental chemical processes in solvated systems including molecular transport, proton transfer, and electronic excitation. This theoretical research will lead to an improved understanding of the factors which influence chemical reactions in solution.