Electron Transfer Reactions of Molecules with Varied Reorganization Energy

Jack R. Pladziewicz博士，威斯康星大学欧克莱尔分校化学系，由化学系无机、生物无机和有机金属化学项目支持，研究电子转移过程。本研究将测量一系列肼及其自由基阳离子的单电子转移反应的速率常数。这些数据将用于评估这些反应在多大程度上符合当前的外层电子转移理论。特别是烷基肼的内壳层重排能和内壳层重排对电子转移反应的激活自由能的贡献程度将被确定。通过使用交叉反应速率常数，可以估计交换速率慢或性质不适合研究的肼的自交换电子转移。许多化学反应涉及电子从一个分子转移到另一个分子。影响这些过程速率的一个尚未被很好地理解的因素是分子在电子与分子之间的转移时所经历的重组。该项目旨在确定一系列含氮有机分子的这些重组的能量，并评估当前理论能够解释重组对电子转移速率的影响的程度。

Dr. Jack R. Pladziewicz, Chemistry Department, University of Wisconsin - Eau Claire, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program of the Chemistry Division to investigate electron transfer processes. In this investigation rate constants will be measured for the single electron transfer reactions of a series of hydrazines and their radical cations. The data will then be used to evaluate the extent to which these reactions fit current theories for outer-sphere electron transfer. In particular the inner-shell reorganization energies for the alkyl hydrazine and the extent to which inner-shell reorganization contributes to the activation free energy for electron transfer reactions will be determined. By use of cross-reaction rate constants the self-exchange electron transfer will be estimated for hydrazines with slow exchange rates or with properties that make them otherwise unamenable to study. Many chemical reactions involve the transfer of electrons from one molecule to a second. One factor which influences the rate of these processes and which is not well understood is the reorganization which a molecule undergoes upon the transfer of an electron to or from it. This project is designed to determine the energies of these reorganizations for a series of nitrogen containing organic molecules and to assess how well current theories are able to account for the influence of the reorganization on the electron transfer rate.