Evolution of molecular dissociation through an electronic curve crossing: Polarized emission spectroscopy of CH3I at 266 nm
Evolution of molecular dissociation through an electronic curve crossing: Polarized emission spectroscopy of CH3I at 266 nm
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DOI：
10.1063/1.458116
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发表时间：
1990-01
影响因子：
4.4
通讯作者：
K. Lao;M. Person;P. Xayariboun;L. Butler
中科院分区：
文献类型：
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作者：
K. Lao;M. Person;P. Xayariboun;L. Butler
本文用偏振发射光谱技术研究了CH_3 I分子在耦合排斥电子势能面上的解离。我们在266 nm处激发CH 3 I，并通过相对于激发激光的偏振方向的频率和角分布来分散从解离分子发射的光子。因此，我们测量的偏振的第一个12 C-I伸缩发射功能，对应于266和317 nm之间的光谱区域。我们还获得了旋转包络选定的发射功能，在更高的分辨率扫描和模型的线形参数来自偏振结果。偏振测量表明，进入前几个低位C-I伸缩振动能级的发射是通过平行于吸收的跃迁矩，与3Q 0（2A 1）排斥表面的激发和发射一致。发射到更高的C-I伸缩泛音显示出越来越多的贡献，从发射vi…
We present a study of the dissociation of CH3I on coupled repulsive electronic potential energy surfaces by the technique of polarized emission spectroscopy. We excite CH3I at 266 nm and disperse the photons emitted from the dissociating molecule by both frequency and angular distribution with respect to the polarization direction of the excitation laser. We thus measure the polarization of the first 12 C–I stretching emission features, corresponding to the spectral region between 266 and 317 nm. We also obtain the rotational envelope of selected emission features in higher resolution scans and model the lineshapes with parameters derived from the polarization results. The polarization measurements show the emission into the first few low‐lying C–I stretching vibrational levels is via a transition moment parallel to the absorbing one, consistent with excitation to and emission from the 3Q0(2A1) repulsive surface. Emission to higher C–I stretching overtones shows an increasing contribution from emission vi...