Electric Field Effects on Excited State and Electron Transfer Dynamics

该奖项由无机，生物无机和有机化学计划支持斯蒂芬G。斯坦福大学的Boxer继续研究光谱方法的发展，这种方法可以探测由相对较长的间隔基团分隔的分子片段之间的相互作用。 斯塔克效应光谱用于提供与光谱跃迁相关的电荷位移的大小和方向的定量信息。 外加电场对电子或振动跃迁的影响被用来产生对键合的更深入的理解，特别是在配位络合物中，以及振动频率偏移可以是复杂系统（如蛋白质）中静电效应的定量探针的概念。 初步结果表明，振动斯塔克光谱可以是一个强大的和微创的方法，用于获得信息的蛋白质静电场如何改变改性蛋白质和催化过程中。 这项工作开始概述如何电场可以用来操纵电子和质子转移的速率作为生化反应创建，消耗或取代电偶极子。 不寻常的和特征的非经典斯塔克效应预计会发生在混合价复合物，表现出多个状态，其能量差的影响所施加的电场。 分析这些不寻常的谱线形状将提供这些分子中能量、电子耦合和电荷位移的定量信息。一种新形式的光谱学将用于研究电场如何影响化学、光化学和生物化学过程中的电子、质子和偶极子运动。

This award by the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professor Stephen G. Boxer of Stanford University to continue studies on the development of spectroscopic methods that probe interactions between molecular fragments separated by relatively long spacer groups. Stark effect spectroscopy is used to provide quantitative information on the magnitude and direction of charge displacement associated with a spectroscopic transition. The effect of an applied electric field on an electronic or vibrational transition is used to generate a deeper understanding of bonding, especially in coordination complexes, and the concept that the vibrational frequency shifts can be a quantitative probe for electrostatic effects in complex systems such as proteins. Initial results indicate that vibrational Stark spectroscopy can be a powerful and minimally invasive approach for obtaining information on how protein electrostatic fields change in modified proteins and during catalysis. This work begins to outline how electric fields can be used to manipulate the rates of electron and proton transfer as biochemical reactions create, consume or displace electric dipoles. Unusual and characteristic non-classical Stark effects are expected to occur in mixed-valence complexes that exhibit multiple states whose energy difference is affected by the applied field. Analyses of the resulting unusual line shapes will give quantitative information on the energetics, electronic coupling and charge displacement in these molecules.A new form of spectroscopy will be used to study how electric fields affect electron, proton and dipole movements in chemical, photochemical and biochemical processes.