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Title: Photodissociation dynamics of nitrobenzene and o-nitrotoluene

Abstract

Photodissociation of nitrobenzene at 193, 248, and 266 nm and o-nitrotoluene at 193 and 248 nm was investigated separately using multimass ion imaging techniques. Fragments corresponding to NO and NO{sub 2} elimination from both nitrobenzene and o-nitrotoluene were observed. The translational energy distributions for the NO elimination channel show bimodal distributions, indicating two dissociation mechanisms involved in the dissociation process. The branching ratios between NO and NO{sub 2} elimination channels were determined to be NO/NO{sub 2}=0.32{+-}0.12 (193 nm), 0.26{+-}0.12 (248 nm), and 0.4{+-}0.12(266 nm) for nitrobenzene and 0.42{+-}0.12(193 nm) and 0.3{+-}0.12 (248 nm) for o-nitrotoluene. Additional dissociation channels, O atom elimination from nitrobenzene, and OH elimination from o-nitrotoluene, were observed. New dissociation mechanisms were proposed, and the results are compared with potential energy surfaces obtained from ab initio calculations. Observed absorption bands of photodissociation are assigned by the assistance of the ab initio calculations for the relative energies of the triplet excited states and the vertical excitation energies of the singlet and triplet excited states of nitrobenzene and o-nitrotoluene. Finally, the dissociation rates and lifetimes of photodissociation of nitrobenzene and o-nitrotoluene were predicted and compared to experimental results.

Authors:
; ; ; ;  [1];  [2];  [2];  [3]
  1. Institute of Atomic and Molecular Sciences, Academia Sinica, P.O. Box 23-166, Taipei, Taiwan (China)
  2. (United States)
  3. (China)
Publication Date:
OSTI Identifier:
20991220
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 126; Journal Issue: 6; Other Information: DOI: 10.1063/1.2435351; (c) 2007 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION; BRANCHING RATIO; DISSOCIATION; ENERGY SPECTRA; EXCITED STATES; NITRIC OXIDE; NITROBENZENE; NITROGEN DIOXIDE; PHOTOLYSIS; REACTION KINETICS

Citation Formats

Lin, Ming-Fu, Lee, Yuan T., Ni, Chi-Kung, Xu, Shucheng, Lin, M. C., Department of Chemistry, Emory University, Atlanta, Georgia 30322, Department of Chemistry, Emory University, Atlanta, Georgia 30322, and Center for Interdisciplinary Molecular Science, National Chiao Tung University, Hsinchu, Taiwan. Photodissociation dynamics of nitrobenzene and o-nitrotoluene. United States: N. p., 2007. Web. doi:10.1063/1.2435351.
Lin, Ming-Fu, Lee, Yuan T., Ni, Chi-Kung, Xu, Shucheng, Lin, M. C., Department of Chemistry, Emory University, Atlanta, Georgia 30322, Department of Chemistry, Emory University, Atlanta, Georgia 30322, & Center for Interdisciplinary Molecular Science, National Chiao Tung University, Hsinchu, Taiwan. Photodissociation dynamics of nitrobenzene and o-nitrotoluene. United States. doi:10.1063/1.2435351.
Lin, Ming-Fu, Lee, Yuan T., Ni, Chi-Kung, Xu, Shucheng, Lin, M. C., Department of Chemistry, Emory University, Atlanta, Georgia 30322, Department of Chemistry, Emory University, Atlanta, Georgia 30322, and Center for Interdisciplinary Molecular Science, National Chiao Tung University, Hsinchu, Taiwan. Wed . "Photodissociation dynamics of nitrobenzene and o-nitrotoluene". United States. doi:10.1063/1.2435351.
@article{osti_20991220,
title = {Photodissociation dynamics of nitrobenzene and o-nitrotoluene},
author = {Lin, Ming-Fu and Lee, Yuan T. and Ni, Chi-Kung and Xu, Shucheng and Lin, M. C. and Department of Chemistry, Emory University, Atlanta, Georgia 30322 and Department of Chemistry, Emory University, Atlanta, Georgia 30322 and Center for Interdisciplinary Molecular Science, National Chiao Tung University, Hsinchu, Taiwan},
abstractNote = {Photodissociation of nitrobenzene at 193, 248, and 266 nm and o-nitrotoluene at 193 and 248 nm was investigated separately using multimass ion imaging techniques. Fragments corresponding to NO and NO{sub 2} elimination from both nitrobenzene and o-nitrotoluene were observed. The translational energy distributions for the NO elimination channel show bimodal distributions, indicating two dissociation mechanisms involved in the dissociation process. The branching ratios between NO and NO{sub 2} elimination channels were determined to be NO/NO{sub 2}=0.32{+-}0.12 (193 nm), 0.26{+-}0.12 (248 nm), and 0.4{+-}0.12(266 nm) for nitrobenzene and 0.42{+-}0.12(193 nm) and 0.3{+-}0.12 (248 nm) for o-nitrotoluene. Additional dissociation channels, O atom elimination from nitrobenzene, and OH elimination from o-nitrotoluene, were observed. New dissociation mechanisms were proposed, and the results are compared with potential energy surfaces obtained from ab initio calculations. Observed absorption bands of photodissociation are assigned by the assistance of the ab initio calculations for the relative energies of the triplet excited states and the vertical excitation energies of the singlet and triplet excited states of nitrobenzene and o-nitrotoluene. Finally, the dissociation rates and lifetimes of photodissociation of nitrobenzene and o-nitrotoluene were predicted and compared to experimental results.},
doi = {10.1063/1.2435351},
journal = {Journal of Chemical Physics},
number = 6,
volume = 126,
place = {United States},
year = {Wed Feb 14 00:00:00 EST 2007},
month = {Wed Feb 14 00:00:00 EST 2007}
}