Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Stereodynamics of O(1D) and O(3P) Reactions Studied via Doppler-Resolved Polarization Spectroscopy
Yo FujimuraHiroshi TsurumakiOkitsugu Kajimoto
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2002 Volume 75 Issue 11 Pages 2309-2336

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Abstract

Studies on stereodynamics of the gas-phase elementary reactions of atomic oxygen, O(1D) and O(3P), with simple molecules are reviewed. The angular correlations among the relative velocity vectors of reactants (k) and products (k′), and the product rotational angular momentum vector (j′) have been investigated via Doppler-resolved polarization spectroscopy. In the O(1D) reactions with hydrocarbons and water, OH products are scattered into wide angular range and rotate mainly in the kk′ scattering plane. These angular distributions suggest the formation of an H–O–X (X = C or O) bond in reactive intermediates. By contrast, the NO products of the O(1D) reaction with N2O have isotropic angular distribution of j′, which indicates the participation of the out-of-plane motion in addition to the in-plane motions within the complex. These trends of O(1D) reactions are consistent with the feature of product-state distribution of the individual reactions. Similar analyses for the reactions of O(3P) atom with hydrocarbons have revealed that these reactions are not always dominated by the simple rebound abstraction mechanism based on the triatomic picture, which has long been assumed. As a background of the titled study, this account reviews the progress in the studies on gas-phase chemical reaction dynamics and presents the theory and techniques to investigate the stereodynamics of bimolecular reactions.

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© 2002 The Chemical Society of Japan
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