Femtosecond Photoelectron Imaging on Pyrazine: S1 → T1 Intersystem Crossing and Rotational Coherence Transfer
Femtosecond Photoelectron Imaging on Pyrazine: S1 → T1 Intersystem Crossing and Rotational Coherence Transfer
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DOI：
10.1021/jp0484985
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发表时间：
2004-07
影响因子：
2.9
通讯作者：
M. Tsubouchi;B. J. Whitaker;Toshinori Suzuki
中科院分区：
文献类型：
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作者：
M. Tsubouchi;B. J. Whitaker;Toshinori Suzuki
飞秒时间分辨光电子成像 (TR-PEI) 通过 S1 态应用于吡嗪 (1,4-二氮苯) 的 (1 + 2’) 共振增强多光子电离。研究了从 S1 (nπ*) 到 T1 (nπ*) 态的系间跨越 (ISC) 以及 3s 和 3pz Rydberg 态的电离动力学。详细分析了在 ISC 填充的 T1 态以及光学制备的 S1 态的时间分辨光电子强度中观察到的旋转复活特征。发现 T1 状态下旋转复活时间的对准比 S1 状态下的对准小得多。提出了使用分子本征态基础并考虑角动量耦合的数值计算，以模拟 S1 和 T1 态之间的相干性转移。计算出的信号强度和轴对准的时间依赖性与观察到的轮廓非常一致。 T1 中对齐的减少可以通过角度来解释...
Femtosecond time-resolved photoelectron imaging (TR-PEI) is applied to the (1 + 2‘) resonance-enhanced multiphoton ionization of pyrazine (1,4-diazabenzene) via the S1 state. The intersystem crossing (ISC) from the S1 (nπ*) to the T1 (nπ*) state and the ionization dynamics from 3s and 3pz Rydberg states are investigated. Rotational revival features, observed in the time-resolved photoelectron intensities from the T1 state populated by ISC as well as from the optically prepared S1 state, are analyzed in detail. The alignment at the rotational revival time in the T1 state is found to be much smaller than that in the S1 state. Numerical calculations, using the molecular eigenstate basis and taking account of the angular momentum coupling, to model the transfer of coherence between the S1 and T1 states are presented. The calculated time dependence of signal strength and the axis alignment are found to be in excellent agreement with the observed profiles. The diminished alignment in T1 is explained by the angu...