COMPUTER SIMULATION OF ELECTRON TRANSFER REACTIONS

电子转移(ET)反应在化学反应中起着核心作用 和生物过程。早期的实验和理论 研究已经确定了ET反应和REACH中的关键因素 使用连续统模型进行定性理解 溶剂型。然而，最近的实验提供了详细的 关于信息层面的微观性质的实际 供体和受体的环境可能是非常重要的。这个 这项建议的基本目标是为实现更 溶液和蛋白质中ET反应的微观描述 使用实际的分子模拟。提出了模拟ET的方法 几个关键实验系统中的反应，重点是 理论和实验之间的详细关联 结果。我们建议的模拟研究将包括 以下项目：(I)微观相关性研究 在能量和相应的溶剂的活化之间 Et在溶液中的重组能和自由能 在蛋白质中。将致力于研究 化学修饰的蛋白质(如Ru-细胞色素c)。(Ii) Et反应中动力学效应的微观模拟 将速率常数与介电材料相关联的目标 给定微环境的松弛时间。(Iii) 分子内Franck-Condon活化的计算 高放热反应中的障碍。(四)大力推进 致力于详细的能量学和动力学研究 细菌光合作用中的ET过程。这个项目将尝试 使用X射线结构或反应中心来评估 相关电荷转移态的能量，并探索 蛋白质偶极子涨落的影响。(V)氧化还原 电子转移蛋白的潜力将由FREE进行评估 能量摄动法。这项研究将包括计算 基因修饰对氧化还原电位的影响。

Electron Transfer (ET) reactions play a central role in chemical and biological processes. Early experimental and theoretical studies have identified the key factors in ET reactions and reach a qualitative understanding using a continuum model for the solvent. However, recent experiments are providing detailed information on the level where the microscopic nature of the actual environment of the donor and acceptor might be very important. The basic objective of this proposal is to contribute toward a more microscopic description of ET reactions in solution and proteins using actual molecular simulation. It is proposed to simulate ET reactions in several key experimental systems, focusing on the detailed correlation between the theoretical and experimental results. Our proposed simulation studies will include the following projects: (i) Studies of the microscopic correlation between activation from energies and the corresponding solvent reorganization energies and free energies for ET in solution and in proteins. Significant effort will be dedicated to studies of chemically modified proteins (e.g. Ru-cytochrome c). (ii) Microscopic simulation of dynamical effects in ET reactions, with the goal of correlating rate constants with the dielectric relaxation times of the given microenvironments. (iii) Calculations of the intramolecular Franck-Condon activation barriers in highly exothermic reactions. (iv) A major effort will be dedicated to studies of the detailed energetics and dynamics of ET processes in bacterial photosynthesis. This project will try to use the X-ray structure or the reaction center to evaluate the energies of relevant charge transfer states and to explore the effects of the fluctuations of the protein dipoles. (v) The redox potential of electron transfer proteins will be evaluated by free energy perturbation methods. This study will include calculations of the effects of genetic modifications on redox potentials.