Complex and Sustained Quantum Beating Patterns in a Classic IVR System: The 3151 Level in S1 p-Difluorobenzene
Complex and Sustained Quantum Beating Patterns in a Classic IVR System: The 3151 Level in S1 p-Difluorobenzene
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DOI：
10.1021/jz501135b
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发表时间：
2014-07-17
影响因子：
5.7
通讯作者：
Reid, Katharine L.
中科院分区：
文献类型：
--
作者：
Midgley, Jonathan;Davies, Julia A.;Reid, Katharine L.
利用皮秒时间分辨光电子成像技术，研究了对二氟苯中3（1）5（1）能级激发后的分子内振动能量再分配（IVR）动力学。我们的技术，它具有上级的时间分辨率，早期的研究，但保留足够的能量分辨率，以确定个别振动状态的行为，使我们能够确定六个不同的拍周期的光电子强度，只有其中之一已被观察到以前。分析表明，IVR动力学仅限于少数振动能级，尽管相对较高的激发能。这被推断为是对二氟苯的高度对称性和刚性结构的结果。
Using picosecond time-resolved photoelectron imaging, we have studied the intramolecular vibrational energy redistribution (IVR) dynamics that occur following the excitation of the 3(1)5(1) level, which lies 2068 cm(-1) above the S-1 origin in p-difluorobenzene. Our technique, which has superior time resolution to that of earlier studies but retains sufficient energy resolution to identify the behavior of individual vibrational states, enables us to determine six distinct beating periods in photoelectron intensity, only one of which has been observed previously. Analysis shows that the IVR dynamics are restricted among only a handful of vibrational levels, despite the relatively high excitation energy. This is deduced to be a consequence of the high symmetry and rigid structure of p-difluorobenzene.