Yi-Ping Chang, Tadas Balciunas, Zhong Yin, Marin Sapunar, Bruno N. C. Tenorio, Alexander C. Paul, Shota Tsuru, Henrik Koch, Jean-Pierre Wolf, Sonia Coriani, Hans Jakob Wörner
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引用次数: 0
摘要
分子电子结构的动态重排可以由不同的现象驱动,包括核运动、电子相干性或电子相关性。记录这种电子动力学并确定其在水溶液中的命运一直是一个挑战。在这里,我们利用 X 射线光谱揭示了孤立的吡嗪分子和溶解的吡嗪分子中通过锥形交叉点的电子弛豫引起的电子动力学。我们发现,随之产生的动态与围绕芳香环的电子结构的循环重排相对应。此外,我们还发现,当吡嗪溶于水时,这种电子动力学完全被抑制。我们的观察结果证实,锥形交叉点可以产生不被泵脉冲直接激发的电子动力学,而水溶解可以在不到 40 fs 的时间内消除这些电子动力学。这些结果对研究光诱导分子动力学过程中产生的电子动力学具有重要意义,并揭示了它们对水溶解的敏感性。
Electronic dynamics created at conical intersections and its dephasing in aqueous solution
A dynamical rearrangement in the electronic structure of a molecule can be driven by different phenomena, including nuclear motion, electronic coherence or electron correlation. Recording such electronic dynamics and identifying its fate in an aqueous solution has remained a challenge. Here, we reveal the electronic dynamics induced by electronic relaxation through conical intersections in both isolated and solvated pyrazine molecules using X-ray spectroscopy. We show that the ensuing created dynamics corresponds to a cyclic rearrangement of the electronic structure around the aromatic ring. Furthermore, we found that such electronic dynamics were entirely suppressed when pyrazine was dissolved in water. Our observations confirm that conical intersections can create electronic dynamics that are not directly excited by the pump pulse and that aqueous solvation can dephase them in less than 40 fs. These results have implications for the investigation of electronic dynamics created during light-induced molecular dynamics and shed light on their susceptibility to aqueous solvation.
期刊介绍:
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