Andres Tehlar, Jakob T. Casanova, Andrey Dnestryan, Frank Jensen, Lars Bojer Madsen, Oleg I. Tolstikhin, Hans Jakob Wörner
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引用次数: 0
摘要
高次谐波光谱学是一种全光学技术,具有固有的阿秒级时间分辨率,已成功用于重建电荷迁移、电子隧道动力学和锥形交汇动力学。在这里,我们展示了高次谐波光谱学的两个关键组成部分,即脉冲对准和多驱动波长测量在 1,3-环己二烯和苯中的应用。对于 1,3-环己二烯,我们发现当使用 800 纳米驱动器时,最大和最小发射高次谐波强度的时序与配准脉冲和探针脉冲之间延迟的函数关系在 25 至 30 eV 之间发生倒转,在 35 至 40 eV 之间再次发生倒转,但使用 1420 纳米驱动器时没有观察到倒转。根据弱场渐近理论和精确的光复组合矩阵元素进行的计算证明,这一观察结果可以用多个分子轨道(HOMO 到 HOMO-3)的发射干扰波长来解释。这些结果表明,1,3-环己二烯阳离子中发生了attosecond电荷迁移,并有可能在额外测量的帮助下进行重建。我们的实验还为研究 1,3-环己二烯分子框架内的光化学反应提供了一条途径。
High-harmonic spectroscopy of impulsively aligned 1,3-cyclohexadiene: Signatures of attosecond charge migration
High-harmonic spectroscopy is an all-optical technique with inherent attosecond temporal resolution that has been successfully employed to reconstruct charge migration, electron-tunneling dynamics, and conical-intersection dynamics. Here, we demonstrate the extension of two key components of high-harmonic spectroscopy, i.e., impulsive alignment and measurements with multiple driving wavelengths to 1,3-cyclohexadiene and benzene. In the case of 1,3-cyclohexadiene, we find that the temporal sequence of maximal and minimal emitted high-harmonic intensities as a function of the delay between the alignment and probe pulses inverts between 25 and 30 eV and again between 35 and 40 eV when an 800-nm driver is used, but no inversions are observed with a 1420-nm driver. This observation is explained by the wavelength-dependent interference of emission from multiple molecular orbitals (HOMO to HOMO-3), as demonstrated by calculations based on the weak-field asymptotic theory and accurate photorecombination matrix elements. These results indicate that attosecond charge migration takes place in the 1,3-cyclohexadiene cation and can potentially be reconstructed with the help of additional measurements. Our experiments also demonstrate a pathway toward studying photochemical reactions in the molecular frame of 1,3-cyclohexadiene.