https://doi.org/10.1007/s100530050200
Reaction dynamics of Cl + O3 → ClO + O2
Technische Universität Braunschweig, Institut für Physikalische und
Theoretische Chemie, Hans-Sommer-Strasse 10,
38106 Braunschweig, Germany
Corresponding author: a K.gericke@tu-bs.de
Received:
27
February
1998
Revised:
1
April
1998
Accepted:
15
April
1998
Published online: 15 November 1998
Applying the two photon laser induced fluorescence technique for nascent state resolved
ClO(
) detection, the reaction dynamics of
Cl+O
ClO+O2 is investigated. The ClO product is formed in its
electronic ground state ClO(
). A complete product state analysis in
terms of vibration, rotation, spin-orbit and Λ-states indicates that nascent
ClO radicals are formed in v= 0-6 vibrational states peaking at v=3. The ClO
fragment shows a moderate rotational excitation, described by a Boltzmann distribution
with a temperature parameter of 1300 K ± 200 K. The spin orbit ratio of
:
. Most of the excess energy is
released as translational energy or as internal energy of the O2 product. By
comparing our results with the trajectory studies of
Farantos and Murrell, we favour a
reaction mechanism, where the transition complex is planar containing an essentially
linear OOCl group. In order to determine the possible influence of vibrationally
excited ClO on other trace components of the atmosphere, especially the reaction
ClO(v> 0)+ O3, a rough estimate of the vibrational relaxation rate of ClO with
the major atmospheric collision partner, N2, has been performed. A measurement of
the vibrational distribution of ClO at different N2 pressures indicates a mean
vibrational relaxation rate of 
.
PACS: 34.50.Lf – Chemical reactions, energy disposal, and angular distribution, as studied by atomic and molecular beams / 82.20.Hf – Mechanisms and product distribution / 94.10.Fa – Atmospheric composition (atomic or molecular), chemical reactions and processes
© EDP Sciences, Società Italiana di Fisica, Springer-Verlag, 1998
