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Temperature induced mobility and recombination of atomic oxygen in crystalline Kr and Xe. I. Experiment
 

Summary: Temperature induced mobility and recombination of atomic oxygen
in crystalline Kr and Xe. I. Experiment
A. V. Danilychev and V. A. Apkarian
Department of Chemistry, University of California, Irvine, California 92717
(Received 20 July 1993;accepted20 August 1993)
Recombinant molecular spectra of O2 in crystalline Kr and Xe, obtained from sudden recom-
bination induced by laser pumping of the predissociativeB state, and by adiabatic recombina-
tion induced thermally, are reported.All electronic statesthat correlatewith O( 3P)+O(3P) are
populated by both methodsin Kr. The excited triplet statesare strongly perturbed in Xe. Laser
induced fluorescence(LIF) spectraof atomic 0 are also reported. Two emissionsare observed
in Kr; one at 563 nm with a radiative lifetime of 11ps, and another at 599 nm with a radiative
lifetime of 1.4ps. Theseare assignedto emissionsfrom neutral 0(`S) trapped in substitutional
and interstitial octahedralsites,respectively.0 atoms are generatedin situ by photodissociation
of either O2 or NzO. The subsequentthermally induced recombination of atoms is followed
using LIF from atomic centersand molecular thermoluminescence.The recombination follows
first order kinetics, from which it is inferred that atomic mobilities are characterizedby long-
range migration, with migration lengths of >3OOA. Site specific Arrhenius rate constants are
extracted from the analysis of glow curves. Only two sites, interstitial and substitutional O,,
contribute to the glow curvesin crystalline Kr. A third site is presentin crystalline Xe. A broad
distribution of activation energiesis observedin vapor depositedmatrices.

  

Source: Apkarian, V. Ara - Department of Chemistry, University of California, Irvine

 

Collections: Chemistry