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Vibrational Dephasing along the Reaction Coordinate of an Electron Transfer Reaction
Journal of the American Chemical Society ( IF 15.0 ) Pub Date : 2021-09-03 , DOI: 10.1021/jacs.1c01863
Yusuke Yoneda 1 , Bryan Kudisch 2 , Shahnawaz Rafiq 2 , Margherita Maiuri 2 , Yutaka Nagasawa 3 , Gregory D Scholes 2 , Hiroshi Miyasaka 1
Affiliation  

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.

中文翻译:

沿电子转移反应的反应坐标振动移相

近年来,分子振动在光致电子转移 (ET) 反应中的作用引起了广泛的争论。在这项研究中,我们研究了模型 ET 系统中的振动波包动力学,该系统由溶解在各种给电子溶剂中的有机染料分子作为电子受体组成。通过使用宽带泵浦探针 (BBPP) 光谱和持续时间低于 10 fs 的可见激光脉冲,频率范围为 170–1600 cm –1的并四苯染料的相干振动波包在时域中观察到。通过逆傅立叶滤波程序分析了 11 种振动模式的相干特性,我们发现一些振动相干的相干时间随着 ET 率的增加而减少。密度泛函理论计算表明,相应的振动模式在反应物和产物状态之间有一个很大的 Huang-Rhys 因子,支持了这样的假设,即沿某些振动模式的相相干性丧失表明这些振动与反应物的反应坐标耦合。 ET反应。
更新日期:2021-09-15
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