Probing the origins of vibrational mode specificity in intramolecular dynamics through picosecond time-resolved photoelectron imaging studies.
Probing the origins of vibrational mode specificity in intramolecular dynamics through picosecond time-resolved photoelectron imaging studies.
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通过皮秒时间分辨光电子成像研究探讨分子内动力学振动模式特异性的起源。
DOI：
10.1039/c6cp08132k
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发表时间：
2017
期刊：
影响因子：
--
通讯作者：
Davies JA
中科院分区：
文献类型：
--
作者：
Davies JA
利用皮秒时间分辨光电子成像技术研究了S1对氟甲苯两个近等能振动态的选择性光激发诱导的分子内动力学。我们发现，在1990 cm−1和2026 cm−1处的13111和7a 111态的制备之后，类似的动力学随之而来，并且在每种情况下，这些动力学都由单个强耦合门口态介导。然而，寿命相差三倍，这表明所涉及模式的振动特征的影响。我们的结果清楚地表明了扭振耦合对动力学的贡献;这一点通过与S1 p-二氟苯中位于2068 cm−1的7a 111态的比较得到了进一步的证实。我们调用一个模型，其中甲基氢原子和附近的环碳和氢原子之间的货车范德华相互作用导致的振动和扭转状态的混合。该模型预测，增强扭转振动耦合时，模式7a被激发，与我们的观察一致。
We have studied the intramolecular dynamics induced by selective photoexcitation of two near-isoenergetic vibrational states in S1p-fluorotoluene using picosecond time-resolved photoelectron imaging. We find that similar dynamics ensue following the preparation of the 13111 and 7a111 states that lie at 1990 cm−1 and 2026 cm−1, and that these dynamics are mediated by a single strongly coupled doorway state in each case. However, the lifetimes differ by a factor of three, suggesting an influence of the vibrational character of the modes involved. Our results clearly show the contribution of torsion-vibration coupling to the dynamics; this is further corroborated by comparison with the 7a111 state in S1p-difluorobenzene, which lies at 2068 cm−1. We invoke a model in which van der Waals interactions between methyl hydrogen atoms and nearby ring carbon and hydrogen atoms leads to mixing of the vibrational and torsional states. This model predicts that enhanced torsion-vibration coupling occurs when mode 7a is excited, consistent with our observations.
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甲基内旋转加速分子内振动重新分布 II。
影响因子：
4.4
作者：
P. Timbers;C. Parmenter;D. Moss
通讯作者：
D. Moss
影响因子：
4.4
作者：
Davies, Julia A.;Reid, Katharine L.
通讯作者：
Reid, Katharine L.
影响因子：
5.7
作者：
Midgley, Jonathan;Davies, Julia A.;Reid, Katharine L.
通讯作者：
Reid, Katharine L.
S1对氟甲苯的激光光电子能谱和动力学
影响因子：
2.9
作者：
S. Bellm;Paul T. Whiteside;K. L. Reid
通讯作者：
K. L. Reid
DOI：
10.1063/1.1668640
发表时间：
2004-04
期刊：
The Journal of chemical physics
影响因子：
--
作者：
Yuji Yamada;T. Ebata;M. Kayano;N. Mikami
通讯作者：
Yuji Yamada;T. Ebata;M. Kayano;N. Mikami