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Interpretations of XeI and XeBr bound--free emission spectra and reactive quenching of Xe(/sup 3/P/sub 2/) atoms by bromine and iodine containing molecules

Journal Article · · J. Chem. Phys.; (United States)
OSTI ID:6582280

The XeBr and XeI emissions spectra have been recorded in a flowing afterglow apparatus from the reaction of Xe(/sup 3/P/sub 2/) atoms with 16 bromine and iodine containing reagents. In all cases both the B and C states of XeI and XeBr are observed; the inital B/C ratio is approx.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 XeC1 emission intensity from Xe(/sup 3/P/sub 2/)+C1/sub 2/ is used to obtain rate constants for XeBr and XeI formation. The branching fractions for XeI and XeBr formation are large, probably unity, for Br/sub 2/, I/sub 2/, IC1, and IBr and relatively small for the polyatomic molecules except for CF/sub 3/I and possible CBr/sub 4/. From the short wavelength limit of the B--X spectra, upper limits to D/sub 0/(R--Br) and D/sub 0/(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 is observed in the C1/sub 2/, Br/sub 2/, I/sub 2/ series and interpreted as evidence for X(/sup 2/P/sub 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(/sup 3/P/sub 2/) with chlorine and fluorine donors.

Research Organization:
Faculty of Pharmaceutical Sciences, Okayama University, Okayama, Japan
OSTI ID:
6582280
Journal Information:
J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 74:8; ISSN JCPSA
Country of Publication:
United States
Language:
English