Interpretations of XeI and XeBr bound-free emission spectra and reactive quenching of Xe(3P2) atoms by bromine and iodine containing molecules

Article abstract of DOI:10.1063/1.441661

The XeBr and XeI emissions spectra have been recorded in a flowing afterglow apparatus from the reaction of Xe(³P₂) atoms with 16 bromine and iodine containing reagent.In all cases both the B and C states of XeI and XeBr are observed; the initial B/C ratio is ca. 1.5.The ratio increase with pressure because of collisional transfer from C to B.Comparison of the total XeBr and XeI emission intensities with the XeCl emission intensity from Xe(³P₂) + Cl2 is used to obtain rate constants for XeBr and XeI formation.The branching fractions for XeI and XeBr formation are large, probably unity, for Br2, I2, ICl, and IBr and relatively small for the polyatomic molecules except for CF3I and possible CBr4.From the short wavelength limit of the B-X spectra, upper limits to D₀(R-Br) and D₀(R-I) are assigned.The theoretical potential curves calculated by Dunning and Hay for the A, B, C, and X states of XeI and XeBr were slightly adjusted so that good agreement was obtained between the simulated and experimental spectra from low vibrational levels of the B and C states.These adjusted potential curves were used to simulate the spectra from high levels of XeBr and XeI, and initial XeBr and XeI vibrational distributions were assigned from matching the low pressure spectra.A systematic decrease in V(XeX)> is observed in the Cl2, Br2, I2 series and interpreted as evidence for X(²P_1/2) formation.The XeBr and XeI vibrational energy disposal is compared to that from reactions of metal atoms with halogen donors and with reactions of Xe(³P₂) with chlorine and fluorine donors.

Full text of DOI:10.1063/1.441661

Interpretations of XeI and XeBr bound–free emission spectra and reactive quenching of
Xe(3 P 2) atoms by bromine and iodine containing molecules
K. Tamagake, D. W. Setser, and J. H. Kolts
Citation: The Journal of Chemical Physics 74, 4286 (1981); doi: 10.1063/1.441661
View online: http://dx.doi.org/10.1063/1.441661
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/74/8?ver=pdfcov
Published by the AIP Publishing
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