Spectroscopic observation of vibrational Feshbach resonances in near-threshold photoexcitation of X-•CH3NO2 (X- = I- and Br-)

被引:41
|
作者
Dessent, CEH
Kim, J
Johnson, MA [1 ]
机构
[1] Univ York, Dept Chem, York YO10 5DD, N Yorkshire, England
[2] Yale Univ, Sterling Chem Lab, New Haven, CT 06520 USA
来源
FARADAY DISCUSSIONS | 2000年 / 115卷
关键词
D O I
10.1039/a909550k
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We report the observation of resonance structure in the absorption and X-/NO2- photofragment action spectra of the X- . CH3NO2 (X- = I- and Br-) complexes in the region above the electron detachment threshold. The resonance structure corresponds to peaks which appear at the onsets for vibrational excitation of the -NO2 wag, scissors, and stretch modes of neutral CH3NO2, the modes which most strongly distort upon electron capture into its pi* lowest unoccupied molecular orbital. We attribute the peaks to excitation of vibrational Feshbach resonances of the CH3NO2- transient negative ion, where near-threshold excitation of X- . CH3NO2 spectroscopically accesses states of the free electron-CH3NO2 system.
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页码:395 / 406
页数:12
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