论文标题

Attsond Xuv探测振动量子叠加的br $ _2^+$

Attosecond XUV probing of vibronic quantum superpositions in Br$_2^+$

论文作者

Kobayashi, Yuki, Neumark, Daniel M., Leone, Stephen R.

论文摘要

超快激光激发可以在分子中产生电子状态的相干叠加,并在几个至子秒的时间尺度上触发电子密度的超快流动。虽然最近的Attsond实验已经解决了对这些主要光化学过程的实时观察,但同时核运动的潜在作用以及它们如何修改和干扰价电子运动仍不确定。在这里,我们使用Attsond Transient Pransient吸收光谱光谱光谱光谱光谱光谱光谱光谱学研究了在多种振动水平的离子溴(BR $ _2^+$)中引起的相干电子振动动力学(BR $ _2^+$)。电子相干的衰减,复兴和明显的频移是通过在br- $ 3D $核心级吸收信号上的特征量子拍打来测量的。量子力学模拟将观察到的电子破裂性归因于核波包的扩大相位分布在非谐电势上。进一步揭示了分子振动结构被烙印为电子节拍频率中的离散进程。这些结果为解释多原子系统中复杂的电荷迁移动态提供了未来的基础。

Ultrafast laser excitation can create coherent superpositions of electronic states in molecules and trigger ultrafast flow of electron density on few- to sub-femtosecond time scales. While recent attosecond experiments have addressed real-time observation of these primary photochemical processes, the underlying roles of simultaneous nuclear motions and how they modify and disturb the valence electronic motion remain uncertain. Here, we investigate coherent electronic-vibrational dynamics induced among multiple vibronic levels of ionic bromine (Br$_2^+$), including both spin-orbit and valence electronic superpositions, using attosecond transient absorption spectroscopy. Decay, revival, and apparent frequency shifts of electronic coherences are measured via characteristic quantum beats on the Br-$3d$ core-level absorption signals. Quantum-mechanical simulations attribute the observed electronic decoherence to broadened phase distributions of nuclear wave packets on anharmonic potentials. Molecular vibronic structure is further revealed to be imprinted as discrete progressions in electronic beat frequencies. These results provide a future basis to interpret complex charge-migration dynamics in polyatomic systems.

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