Electric Field Effects on Excited State and Electron Transfer Dynamics

电场对激发态和电子转移动力学的影响

• 批准号: 9303109
• 负责人: Steven Boxer
• 金额: $ 35.32万
• 依托单位: Stanford University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1993
• 资助国家: 美国
• 起止时间: 1993-06-15 至 1996-11-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9303109&HistoricalAwards=false
• 关键词: Electric; Field; Effects; Excited; State

Professor Boxer of Stanford University will use Stark effect spectroscopy to investigate charge-transfer processes in simple molecules, with support from the Inorganic, Bioinorganic, and Organometallic Chemistry Program. The technique entails subjecting the sample (a thin film containing the molecule of interest) to a high and variable electric field, and observing the effect of the field on the absorption or emission of light. Characteristic lineshapes are obtained that yield information regarding the relationship between the transition dipole and the molecular axes. Processes to be investigated include LMCT transitions, intramolecular electron transfer reactions, proton transfer reactions, and vibrational transitions. Of particular interest is the influence of driving force on electron transfer rates. Molecules to be investigated include coordination complexes such as tris(bipyradyl)ruthenium(II) ion and related mixed-valence species, covalently-linked benzophenone/naphthalene derivatives, porphyrin/quinone species, certain rhenium complexes, and bromobenzene. This new technique should add an important new dimension in the understanding of molecular dynamics. %%% A particularly nettlesome problem is to understand the flow of charge within molecules. For example, if a molecule absorbs a photon of visible light, how do the electrons within the molecule respond spatially? Professor Boxer has developed a potentially powerful new technique, called Stark effect spectroscopy, to answer such questions. Essentially, the molecules are subjected to high electric fields while their interactions with light are measured. The results to be obtained will reveal how different parts of a molecule "communicate" and will improve understanding of the charge-separation processes so important in photosynthesis and related phenomena.

斯坦福大学的鲍克瑟教授将利用斯塔克效应 光谱研究电荷转移过程中简单 分子，支持无机，生物无机，和 有机化学课程。 这项技术需要 使样品（含有以下分子的薄膜） 感兴趣）到高且可变的电场，并观察 场对光的吸收或发射的影响。 特征线的形状得到的产量信息 关于跃迁偶极子和 分子轴 待调查的工艺包括LMCT 跃迁，分子内电子转移反应，质子 转移反应和振动跃迁。 特别 感兴趣的是驱动力对电子转移的影响 rates. 要研究的分子包括配位 络合物如三（联吡啶基）钌（II）离子和相关的 混合价态物质，共价连接的 二苯甲酮/萘衍生物，卟啉/醌 物种，某些化合物和溴苯。 这个新 这项技术应该在这个领域增加一个重要的新维度， 了解分子动力学。 %%% 一个特别令人恼火的问题是要了解 分子中的电荷 例如，如果一个分子吸收了 可见光的光子， 分子空间响应？ 鲍克瑟教授发明了一种 一种潜在的强大的新技术，称为斯塔克效应 光谱学来回答这些问题。 本质上 分子受到高电场的作用， 测量与光的相互作用。 报告的结果 将揭示一个分子的不同部分 “沟通”并将提高对 电荷分离过程在光合作用中非常重要， 相关现象。