Determination of the internal state distribution of NO produced from the H + NO2 reaction

Article abstract of DOI:10.1063/1.457981

The internal state distribution of the NO product from the H + NO2 reaction was determined in a crossed-beam experiment.Rotational populations in the υ = 0 to 2 vibrational levels of NO were derived from laser fluorescence excitation spectra of the A²Σ⁺ -X²Π band system.The vibrational distribution decreases monotonically with υ, and the rotational state distribution is peaked at low J (most probable J of approximately 11.5), but the tail of the distribution extends out to N ca. 50.After correction for the flux-density transformation, the vibrational population distribution is found to equal 1:0.17 +/- 0.04:0.05 +/- 0.02 for υ = 0,1,2, respectively.The lower F₁ (Ω = 1/2) spin-orbit component is preferred over the F₂ (Ω = 3/2) manifold by a ratio of 1:0.52 +/- 0.11, independent of vibrational level.At high J, a preference for the Π(A') Λ doublet levels is observed.Approximately 9.5percent +/- 2percent of the reaction exoergicity is found in NO internal excitation.The NO and previously determined OH internal state distributions are compared with statistical distributions calculated by phase-space theory.The energy disposal in OH is found to be greater than statistical, while the opposite is true for NO, as might be expected in a direct reaction of the type A + BCD -> AB + CD for the new and old bonds, respectively.The Λ doublet preference observed here for the NO product, and previously for the OH product, can be explained by the dissociation of an HONO(<*>X¹A') intermediate.A mechanism for the generation of unequal NO spin-orbit populations, involving nonadiabatic mixing in the exit channel, is proposed.

Full text of DOI:10.1063/1.457981

Determination of the internal state distribution of NO produced from the H+NO2
reaction
Deborah G. Sauder and Paul J. Dagdigian
Citation: The Journal of Chemical Physics 92, 2389 (1990); doi: 10.1063/1.457981
View online: http://dx.doi.org/10.1063/1.457981
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/92/4?ver=pdfcov
Published by the AIP Publishing
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
29.22.67.107 On: Sun, 23 Nov 2014 10:06:08
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
29.22.67.107 On: Sun, 23 Nov 2014 10:06:08
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
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