Internal energy of HCl upon photolysis of 2-chloropropene at 193 nm investigated with time-resolved Fourier-transform spectroscopy and quasiclassical trajectories

Journal Article · Sun Dec 14 04:00:00 EST 2008 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3023149· OSTI ID:21254940

Chang, C -M; Huang, Y -H; Liu, S -Y ^[1]; Lee, Y -P ^[1]; Pombar-Perez, Marta; Martinez-Nunez, Emilio; Vazquez, Saulo A ^[2]

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1. Department of Applied Chemistry, National Chiao Tung University, Hsinchu 30010, Taiwan (China)
2. Departamento de Quimica Fisica, Facultad de Quimica, Universidade de Santiago de Compostela 15782, Santiago de Compostela (Spain)

Following photodissociation of 2-chloropropene (H{sub 2}CCClCH{sub 3}) at 193 nm, vibration-rotationally resolved emission spectra of HCl ({upsilon}{<=}6) in the spectral region of 1900-2900 cm{sup -1} were recorded with a step-scan time-resolved Fourier-transform spectrometer. All vibrational levels show a small low-J component corresponding to {approx}400 K and a major high-J component corresponding to 7100-18 700 K with average rotational energy of 39{+-}{sub 3}{sup 11} kJ mol{sup -1}. The vibrational population of HCl is inverted at {upsilon}=2, and the average vibrational energy is 86{+-}5 kJ mol{sup -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.

• OSTI ID: 21254940
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 22 Vol. 129; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ALLENE
DISSOCIATION
EMISSION SPECTRA
ENERGY SPECTRA
FOURIER TRANSFORM SPECTROMETERS
FOURIER TRANSFORMATION
HYDROCHLORIC ACID
ORGANIC CHLORINE COMPOUNDS
PHOTOLYSIS
SPECTROSCOPY
VINYL CHLORIDE