標題: Internal energy of HCl upon photolysis of 2-chloropropene at 193 nm investigated with time-resolved Fourier-transform spectroscopy and quasiclassical trajectories
作者: Chang, Chih-Min
Huang, Yu-Hsuan
Liu, Suet-Yi
Lee, Yuan-Pern
Pombar-Perez, Marta
Martinez-Nunez, Emilio
Vazquez, Saulo A.
應用化學系
應用化學系分子科學碩博班
Department of Applied Chemistry
Institute of Molecular science
關鍵字: Fourier transform spectra;organic compounds;photodissociation;spectrochemical analysis;time resolved spectra
公開日期: 14-Dec-2008
摘要: Following photodissociation of 2-chloropropene (H(2)CCClCH(3)) at 193 nm, vibration-rotationally resolved emission spectra of HCl (upsilon <= 6) in the spectral region of 1900-2900 cm(-1) were recorded with a step-scan time-resolved Fourier-transform spectrometer. All vibrational levels show a small low-J component corresponding to similar to 400 K and a major high-J component corresponding to 7100-18 700 K with average rotational energy of 39 +/-(11)(3) kJ mol(-1). The vibrational population of HCl is inverted at upsilon=2, and the average vibrational energy is 86 +/- 5 kJ mol(-1). Two possible channels of molecular elimination producing HCl+propyne or HCl+allene cannot be distinguished positively based on the observed internal energy distribution of HCl. The observed rotational distributions fit qualitatively with the distributions of both channels obtained with quasiclassical trajectories (QCTs), but the QCT calculations predict negligible populations for states at small J. The observed vibrational distribution agrees satisfactorily with the total QCT distribution obtained as a weighted sum of contributions from both four-center elimination channels. Internal energy distributions of HCl from 2-chloropropene and vinyl chloride are compared.
URI: http://dx.doi.org/10.1063/1.3023149
http://hdl.handle.net/11536/8031
ISSN: 0021-9606
DOI: 10.1063/1.3023149
期刊: JOURNAL OF CHEMICAL PHYSICS
Volume: 129
Issue: 22
結束頁: 
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