Vibrational promotion of electron transfer
Vibrational promotion of electron transfer
复制标题
DOI：
10.1126/science.290.5489.111
复制
发表时间：
2000-10-06
期刊：
影响因子：
56.9
通讯作者：
Wodtke, AM
中科院分区：
文献类型：
--
作者：
Huang, YH;Rettner, CT;Wodtke, AM
通过使用激光的方法来制备特定的量子态的气相一氧化氮分子，我们研究了振动运动的作用，在电子转移到一个分子从金属表面的溶剂化效应的复杂影响。电子转移过程的特征是一个高效的多量子振动弛豫事件，其中氮氧化物在亚皮秒时间尺度上每摩尔损失数百千焦的能量。这些结果不能简单地用Franck-Condon因子来解释。与处于高振动态的分子相关联的大振幅振动运动强烈地调制电子转移反应的能量驱动力。这些结果显示了分子振动在促进电子转移反应中的重要性，这是一类对分子电子器件、太阳能转换和许多生物过程很重要的化学。
By using laser methods to prepare specific quantum states of gas-phase nitric oxide molecules, we examined the role of vibrational motion in electron transfer to a molecule from a metal surface free from the complicating influence of solvation effects. The signature of the electron transfer process is a highly efficient multiquantum vibrational relaxation event, where the nitrogen oxide loses hundreds of kilojoules per mole of energy on a subpicosecond time scale. These results cannot be explained simply on the basis of Franck-Condon factors. The large-amplitude vibrational motion associated;with molecules in high vibrational states strongly modulates the energetic driving force of the electron transfer reaction. These results show the importance of molecular vibration in promoting electron transfer reactions, a class of chemistry important to molecular electronics devices, solar energy conversion, and many biological processes.