Vibrational Dephasing along the Reaction Coordinate of an Electron Transfer Reaction.
Vibrational Dephasing along the Reaction Coordinate of an Electron Transfer Reaction.
复制标题
沿着电子转移反应的反应坐标的振动相移。
DOI：
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发表时间：
2021
影响因子：
15
通讯作者：
H. Miyasaka
中科院分区：
文献类型：
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作者：
Y. Yoneda;Bryan Kudisch;Shahnawaz Rafiq;M. Maiuri;Yutaka Nagasawa;G. Scholes;H. Miyasaka
近年来，分子振动在光诱导电子转移反应中的作用引起了广泛的争论。在这项研究中，我们研究了振动波包动力学模型ET系统组成的有机染料分子作为电子受体溶解在各种供电子溶剂。利用宽带泵浦-探测（BBPP）光谱技术，在10 fs以下的可见光脉冲作用下，在时域内观测到并四苯染料的相干振动波包，频率范围为170-1600 cm-1。用逆傅里叶滤波方法分析了11个振动模的相干特性，发现某些振动相干的退相时间随ET率的增加而减少。密度泛函理论计算表明，相应的振动模式之间的反应物和产物状态有一个大的黄-里斯因子，支持的假设，相位相干性的损失沿着某些振动模式阐明，这些振动耦合到ET反应的反应坐标。
The role of molecular vibration in photoinduced electron transfer (ET) reactions has been extensively debated in recent years. In this study, we investigated vibrational wavepacket dynamics in a model ET system consisting of an organic dye molecule as an electron acceptor dissolved in various electron donating solvents. By using broad band pump-probe (BBPP) spectroscopy with visible laser pulses of sub-10 fs duration, coherent vibrational wavepackets of naphthacene dye with frequencies spanning 170-1600 cm-1 were observed in the time domain. The coherence properties of 11 vibrational modes were analyzed by an inverse Fourier filtering procedure, and we discovered that the dephasing times of some vibrational coherences are reduced with increasing ET rates. Density functional theory calculations indicated that the corresponding vibrational modes have a large Huang-Rhys factor between the reactant and the product states, supporting the hypothesis that the loss of phase coherence along certain vibrational modes elucidates that those vibrations are coupled to the reaction coordinate of an ET reaction.
影响因子：
18.3
作者：
Beratan, David N.;Skourtis, Spiros S.;Balabin, Ilya A.;Balaeff, Alexander;Keinan, Shahar;Venkatramani, Ravindra;Xiao, Dequan
通讯作者：
Xiao, Dequan