Experimental results for optically controlled electron-transfer reaction kinetics (ETRK) and nonequilibrium solvation dynamics (NESD) of Coumarin 480 in DMPC vesicle show their dependence on excitation wavelength λ_ex. However, the celebrated Marcus theory and linear-response-theory-based approaches for ETRK and NESD, respectively, predict both of the processes to be independent of λ_ex. The above said lacuna in these theories prompted us to develop a novel theory in 1D space, where the effect of innumerable Franck–Condon states is included through λ_ex. The present theory not only sheds light on the origin of failure of the existing theories but also gives the correct trend for the effect of λ_ex on ETRK and NESD. More importantly, the calculated results of NESD are in excellent agreement with the experimental results for different values of λ_ex. The new theory will therefore advance the knowledge of scientific community on the dynamics of photoinduced nonequilibrium processes.

中文翻译：

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光学控制的电子转移反应动力学和溶剂化动力学：弗兰克–康登状态的影响

香豆素480在DMPC囊泡中的光控电子转移反应动力学（ETRK）和非平衡溶剂化动力学（NESD）的实验结果表明，它们依赖于激发波长_λex。然而，著名的Marcus理论和基于线性响应理论的ETRK和NESD方法分别预测这两个过程都与_λex无关。上面说的空隙在这些理论促使我们开发的一维空间，如果国家通过λ包括无数的弗兰克-康登的作用的新理论_前。本理论不仅阐明了现有理论的失败根源，而且给出了_λex效应的正确趋势。在ETRK和NESD上。更重要的是，NESD的计算结果均符合λ的不同值的实验结果非常吻合_前。因此，新理论将促进科学界对光致非平衡过程动力学的认识。