Interplay of vibrational wavepackets during an ultrafast electron transfer reaction
Interplay of vibrational wavepackets during an ultrafast electron transfer reaction
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超快电子转移反应中振动波包的相互作用
DOI：
10.1038/s41557-020-00607-9
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发表时间：
2020-12
期刊：
影响因子：
21.8
通讯作者：
Shahnawaz Rafiq;Bo Fu;Bryan Kudisch;G. Scholes
中科院分区：
文献类型：
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作者：
Shahnawaz Rafiq;Bo Fu;Bryan Kudisch;G. Scholes
电子转移反应促进了生物学和化学中的能量转换和光氧化还原过程。最近的研究表明，分子振动可以使一些电子转移反应的显着加速，并通过抑制和增强反应路径来控制它。在这里，我们报告超快光谱实验和量子动力学模拟，解决量子振动如何参与电子转移反应。我们观察弹道电子转移（~30 fs）沿着反应坐标，包括高频促进振动。沿着另一个振动坐标，系统由于电子转移反应而突然失去平衡。这导致（通过电子转移反应，而不是激光脉冲）沿着该第二反应坐标以与反应产物相关联的模式产生新的振动相干性沿着。这些结果解决了一个复杂的反应轨迹组成的多个振动坐标，像一个序列的棘轮，逐步减少反应物状态的复发。
Electron transfer reactions facilitate energy transduction and photoredox processes in biology and chemistry. Recent findings show that molecular vibrations can enable the dramatic acceleration of some electron transfer reactions, and control it by suppressing and enhancing reaction paths. Here, we report ultrafast spectroscopy experiments and quantum dynamics simulations that resolve how quantum vibrations participate in an electron transfer reaction. We observe ballistic electron transfer (~30 fs) along a reaction coordinate comprising high-frequency promoting vibrations. Along another vibrational coordinate, the system becomes impulsively out of equilibrium as a result of the electron transfer reaction. This leads to the generation (by the electron transfer reaction, not the laser pulse) of a new vibrational coherence along this second reaction coordinate in a mode associated with the reaction product. These results resolve a complex reaction trajectory composed of multiple vibrational coordinates that, like a sequence of ratchets, progressively diminish the recurrence of the reactant state.