Resonance Raman Intensities and Charge-Transfer Reorganization Energies.
Resonance Raman Intensities and Charge-Transfer Reorganization Energies.
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DOI：
10.1021/cr950249c
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发表时间：
1996-05
期刊：
影响因子：
62.1
通讯作者：
A. Myers
中科院分区：
文献类型：
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作者：
A. Myers
当一个分子体系发生电荷转移反应时，反应分子(S)和环境中分子的核的平衡位置通常都会改变。因此，如果反应发生在反应物的平衡几何构型(S)，原子核必须移动才能达到产物的平衡几何构型(S)。这两种结构之间的能量差被称为“重组能”，它可以分解为来自反应分子(S)(“内部”重组)和来自环境(“溶剂”重组)的贡献。内部重组能量可以被进一步划分为来自个体振动的贡献，通常被称为“特定模式”的重组能量。弱耦合(非绝热)极限下电子转移的理论描述通常将反应速率表示为电子矩阵元和核部分的乘积，前者取决于施主和受主的距离和相对取向，后者取决于与跃迁耦合的模式的频率和重组能量。这些重组能传统上被认为是很难通过实验或理论获得的。然而，在反应物和产物之间也存在辐射跃迁的情况下，分析与电荷转移跃迁共振时获得的振动喇曼谱线的强度，原则上可以揭示完整的模式特定重组能量集。这篇文章解释了这种分析的方式和原因，回顾了现有文献中的例子，并提出了可能的未来。安妮·B·迈尔斯1958年5月9日出生于康涅狄格州纽黑文，1961年随家人搬到加利福尼亚州的河滨。她于1980年在加州大学河滨分校获得化学学士学位，并于1984年与Rich Mathies合作在伯克利获得生物物理化学博士学位。在宾夕法尼亚大学与罗宾·霍奇斯特拉瑟一起做了两年的NIH博士后研究之后，她于1987年加入了罗切斯特大学的化学系。她于1990年晋升为副教授，并于1995年晋升为教授。1995年，她还成为光诱导电荷转移中心的主任，这是一个由NSF资助的科学和技术中心，涉及罗切斯特大学、伊士曼柯达和施乐。她的研究兴趣包括快速光化学反应的时间−和频率−域光谱探针、共振拉曼光谱、电子转移和单分子光谱的理论和实践。她获得了帕卡德科学与工程奖学金、美国国家科学基金会总统青年研究员奖和德莱弗斯教师−学者奖，并是70多种出版物的作者。她还喜欢长跑，并有资格参加1992年美国奥运会马拉松选拔赛。
When a molecular system undergoes a chargetransfer reaction, the equilibrium positions of the nuclei of both the reacting molecule (s) and the molecules in the environment generally change. Thus, if the reaction occurs at the equilibrium geometry of the reactant (s), the nuclei have to move in order to reach the equilibrium geometry of the product (s). The difference in energy between these two structures is referred to as the “reorganization energy”, which can be decomposed into its contributions from the reacting molecule (s)(“internal” reorganization) and from the environment (“solvent” reorganization). The internal reorganization energy can be further partitioned into its contributions from individual vibrations, usually referred to as “modespecific” reorganization energies. Theoretical descriptions of electron transfer in the weak coupling (nonadiabatic) limit generally express the reaction rate as a product of an electronic matrix element, which depends on the distance and relative orientation of donor and acceptor, and a nuclear part, which depends on the frequencies and reorganization energies of the modes coupled to the transition. 1-4 These reorganization energies have traditionally been considered very difficult to obtain either experimentally or theoretically. However, in cases where there is also a radiative transition connecting the reactants and products, analysis of the intensities of the vibrational Raman lines obtained on resonance with the charge-transfer transition can, in principle, reveal the complete set of mode-specific reorganization energies. This article explains how and why such analyses are performed, reviews existing examples in the literature, and suggests likely futureAnne B. Myers was born May 9, 1958, in New Haven, CT, but moved with her family to Riverside, CA, in 1961. She earned her BS in chemistry from the University of California, Riverside, in 1980 and her Ph. D. in biophysical chemistry from Berkeley in 1984, working with Rich Mathies. After a two-year NIH postdoctoral fellowship with Robin Hochstrasser at the University of Pennsylvania, she joined the chemistry faculty at the University of Rochester in 1987. She was promoted to Associate Professor in 1990 and to Professor in 1995. In 1995 she also became Director of the Center for Photoinduced Charge Transfer, an NSF-funded Science and Technology Center involving the University of Rochester, Eastman Kodak, and Xerox. Her research interests lie in time− and frequency− domain spectroscopic probes of fast photochemical reactions, the theory and practice of resonance Raman spectroscopy, electron transfer, and single molecule spectroscopy. She has received a Packard Fellowship in Science and Engineering, an NSF Presidential Young Investigator Award, and a Dreyfus Teacher− Scholar award, and is the author of more than 70 publications. She also enjoys distance running and qualified for the US Olympic Trials in the marathon in 1992.