Photoinduced changes in the structure of a van der Waals complex. Three-dimensional inertial axis reorientation in the S1←S0 electronic spectrum of indole-Ar
Photoinduced changes in the structure of a van der Waals complex. Three-dimensional inertial axis reorientation in the S1←S0 electronic spectrum of indole-Ar
复制标题
吲哚-Ar S1←S0 电子谱中范德华配合物结构的光诱导变化。
DOI：
10.1063/1.479734
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发表时间：
1999
影响因子：
4.4
通讯作者：
D. Pratt
中科院分区：
文献类型：
--
作者：
T. Korter;J. Küpper;D. Pratt
本文报道了货车范德华络合物吲哚-Ar和N-氘代吲哚-Ar在气相中的转动分辨S_1 ← S_0电子光谱。这两个光谱表现出惯性轴重定向。从两个光谱的拟合得到的参数与从先前的裸分子研究得到的参数的比较[Berden等人，J.Chem.Phys.103，9596（1995）]表明，吲哚-Ar中的Ar原子连接在吲哚平面上方，在两种电子状态下都向五元环中的N原子移位。然而，测量的质量中心坐标的Ar原子的主轴框架中的吲哚在两个国家是不同的，导致观察到的高分辨率光谱轴重定向。吲哚自身的S1态被证明是1 Lb态，它具有与基态不同的电子分布。因此，Ar原子“移动”时，光子被吸收，因为有显着差异的分子间势能面…
Rotationally resolved S1←S0 electronic spectra of the van der Waals complexes indole-Ar and N-deuterated-indole-Ar in the gas phase are described. Both spectra exhibit inertial axis reorientation. A comparison of the parameters derived from fits of the two spectra with those obtained from a previous study of the bare molecule [Berden et al., J. Chem. Phys. 103, 9596 (1995)] shows that the Ar atom in indole-Ar is attached above the indole plane, displaced toward the N atom in the five-membered ring, in both electronic states. However, the measured center-of-mass coordinates of the Ar atom in the principal axis frames of indole in the two states are different, leading to the observed axis reorientation in the high resolution spectra. The S1 state in indole itself is shown to be the 1Lb state, which has a different electronic distribution from that of the ground state. Thus, the Ar atom “moves” when the photon is absorbed because there are significant differences in the intermolecular potential energy surfac...