Resonant femtosecond stimulated Raman spectroscopy with an intense actinic pump pulse: Application to conical intersections.
Resonant femtosecond stimulated Raman spectroscopy with an intense actinic pump pulse: Application to conical intersections.
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DOI：
10.1063/1.4976317
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发表时间：
2017-02
期刊：
影响因子：
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通讯作者：
B. J. Rao;M. Gelin;W. Domcke
中科院分区：
文献类型：
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作者：
B. J. Rao;M. Gelin;W. Domcke
我们从理论上研究了利用强光化泵浦脉冲的时间分辨共振飞秒受激拉曼光谱（FSRS）来表征圆锥相交的可行性。我们利用吡嗪分子中的S2（ππ*）-S1（nπ*）圆锥相交模型，对三电子态双振动模模型的FSRS信号进行了非微扰数值模拟.我们的研究结果表明，中等强度的光化脉冲增加的FSRS瞬态振动指纹线的强度。它们通过增强揭示锥形交叉的耦合和调谐模式的峰来促进有用的光谱信息的提取。
We theoretically investigate the feasibility of characterizing conical intersections with time-resolved resonant femtosecond stimulated Raman spectroscopy (FSRS) using an intense actinic pump pulse. We perform nonperturbative numerical simulations of FSRS signals for a three-electronic-state two-vibrational-mode model, which is inspired by the S2(ππ*)-S1(nπ*) conical intersection in pyrazine. Our results show that moderately strong actinic pulses increase the intensity of vibrational fingerprint lines in FSRS transients. They facilitate the extraction of useful spectroscopic information by enhancing peaks revealing the coupling and tuning modes of the conical intersection.