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Title: Reactions of hyperthermal C({sup 3}P) generated by laser ablation with H{sub 2} HCl, HBr, and CH{sub 3}OH

Abstract

The reactions of C({sup 3}P) with H{sub 2}, HCl, HBr, and CH{sub 3}OH(D) were investigated in a crossed-beam configuration using laser ablation of graphite as the source of C({sup 3}P). Upon pulsed irradiation of graphite with focused laser output at 266 and 355 nm, hyperthermal C({sup 3}P) is produced and expands freely into the vacuum. Using 266 nm ablation, the endothermic reactions of C({sup 3} P) with the title molecules were investigated by probing the CH product. CH is produced predominantly in v = 0 with rotational distributions that are well described by temperatures in the range 1500-2200 K, depending on the molecular reactants. The spin-orbit and {Lambda}-doublet sublevels are equally populated. In reactions with CH{sub 3}OD, both CH and CD are detected, identifying both the methyl and the hydroxyl groups as reactive sites. Comparisons with the CH internal energy distributions obtained in the reaction of C({sup 1}D) with H{sub 2} show remarkable similarities. On the basis of theoretical investigations and the known electronic states of the methylene intermediate, it is suggested that the reactions of both C({sup 3}P) and C({sup 1}D) proceed via insertion involving carbene intermediates. The participation of several low-lying states of the carbenes may lead bothmore » to lowering of the activation barrier for insertion and to CH products with similar populations of the two {Lambda}-doublet components. 55 refs., 7 figs.« less

Authors:
; ; ;  [1]
  1. Univ. of Southern California, Los Angeles, CA (United States)
Publication Date:
OSTI Identifier:
136281
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry
Additional Journal Information:
Journal Volume: 99; Journal Issue: 40; Other Information: PBD: 5 Oct 1995
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 40 CHEMISTRY; 42 ENGINEERING NOT INCLUDED IN OTHER CATEGORIES; 66 PHYSICS; CARBON; CHEMICAL REACTIONS; GRAPHITE; ABLATION; HYDROGEN; HYDROCHLORIC ACID; HYDROBROMIC ACID; METHANOL; LASERS; ENERGY LEVELS; EMISSION SPECTRA

Citation Formats

Scholefield, M.R., Goyal, S., Choi, J.H., and Reisler, H. Reactions of hyperthermal C({sup 3}P) generated by laser ablation with H{sub 2} HCl, HBr, and CH{sub 3}OH. United States: N. p., 1995. Web. doi:10.1021/j100040a006.
Scholefield, M.R., Goyal, S., Choi, J.H., & Reisler, H. Reactions of hyperthermal C({sup 3}P) generated by laser ablation with H{sub 2} HCl, HBr, and CH{sub 3}OH. United States. doi:10.1021/j100040a006.
Scholefield, M.R., Goyal, S., Choi, J.H., and Reisler, H. Thu . "Reactions of hyperthermal C({sup 3}P) generated by laser ablation with H{sub 2} HCl, HBr, and CH{sub 3}OH". United States. doi:10.1021/j100040a006.
@article{osti_136281,
title = {Reactions of hyperthermal C({sup 3}P) generated by laser ablation with H{sub 2} HCl, HBr, and CH{sub 3}OH},
author = {Scholefield, M.R. and Goyal, S. and Choi, J.H. and Reisler, H.},
abstractNote = {The reactions of C({sup 3}P) with H{sub 2}, HCl, HBr, and CH{sub 3}OH(D) were investigated in a crossed-beam configuration using laser ablation of graphite as the source of C({sup 3}P). Upon pulsed irradiation of graphite with focused laser output at 266 and 355 nm, hyperthermal C({sup 3}P) is produced and expands freely into the vacuum. Using 266 nm ablation, the endothermic reactions of C({sup 3} P) with the title molecules were investigated by probing the CH product. CH is produced predominantly in v = 0 with rotational distributions that are well described by temperatures in the range 1500-2200 K, depending on the molecular reactants. The spin-orbit and {Lambda}-doublet sublevels are equally populated. In reactions with CH{sub 3}OD, both CH and CD are detected, identifying both the methyl and the hydroxyl groups as reactive sites. Comparisons with the CH internal energy distributions obtained in the reaction of C({sup 1}D) with H{sub 2} show remarkable similarities. On the basis of theoretical investigations and the known electronic states of the methylene intermediate, it is suggested that the reactions of both C({sup 3}P) and C({sup 1}D) proceed via insertion involving carbene intermediates. The participation of several low-lying states of the carbenes may lead both to lowering of the activation barrier for insertion and to CH products with similar populations of the two {Lambda}-doublet components. 55 refs., 7 figs.},
doi = {10.1021/j100040a006},
journal = {Journal of Physical Chemistry},
number = 40,
volume = 99,
place = {United States},
year = {1995},
month = {10}
}