Reactive quenching studies of Xe (6s, /sup 3/P/sub 2/) metastable atoms by chlorine containing molecules

Journal Article · Wed Aug 01 04:00:00 EDT 1979 · J. Chem. Phys.; (United States)

OSTI ID:6050334

Kolts, J H; Velazco, J E; Setser, D W

The XeCl* emission spectrum has been used to study the reactions of Xe (6s, /sup 3/P/sub 2/) metastable atoms with 20 chlorine containing reagents. Although the total quenching rate constants are large, only Cl/sub 2/, the mixed halogens and Group VI chlorides have high product branching fractions for XeCl* excimer formation. From analysis of the low pressure XeCl* emission spectra, the ratios for XeCl (III,1/2 or B,1/2) and XeCl (II,3/2 or C,3/2) formation were determined. Using results presented in the following paper, the vibrational energy distributions of the XeCl* molecules also can be estimated. A wide difference, depending upon reagent, is observed for the vibrational energy disposal. The short wavelength limit of the XeCl (B--X) emission can be used to assign upper limits to D/sup 0//sub 0/ (R--Cl) and this work gives D/sup 0//sub 0/ (SCl--Dl) < or =44.7; D/sup 0//sub 0/ (ClS/sub 2/--Cl) < or =46.2, D/sup 0//sub 0/ (SOCl--Cl) < or =53.9; D/sup 0//sub 0/ (SO/sub 2/--Cl) < or =58.5, and D/sup 0//sub 0/ (PCl/sub 2/--Cl) < or =77.7 kcal mole/sup -1/. For purposes of comparison, the XeCl* emission spectra also were obtained from the reaction of Xe (6s, /sup 3/P/sub 1/) resonance atoms with Cl/sub 2/, PCl/sub 2/, CCl/sub 4/, and COCl/sub 2/. The branching ratios and energy disposal for Xe ( /sup 3/P/sub 2/) and Xe ( /sup 3/P/sub 1/) reactions appear to be qualitatively similar. Based upon all of these data, the dynamics of the reactions between Xe ( /sup 3/P/sub 2/) and the chlorine containing reagents are discussed and compared to the models in the literature used previously for the reactions of alkali metal atoms with halogen containing molecules. Characteristic XeI* and XeBr* spectra from Xe ( /sup 3/P/sub 2/) atom reactions are included in an Appendix.

• Research Organization: Chemistry Department, Kansas State University, Manhattan, Kansas 66506
• OSTI ID: 6050334
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 71:3; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

640304* -- Atomic
Molecular &amp; Chemical Physics-- Collision Phenomena
74 ATOMIC AND MOLECULAR PHYSICS
ATOM COLLISIONS
ATOM-MOLECULE COLLISIONS
CHEMICAL REACTION KINETICS
CHLORIDES
CHLORINE COMPOUNDS
COLLISIONS
DE-EXCITATION
ELEMENTS
EMISSION SPECTRA
ENERGY LEVELS
ENERGY-LEVEL TRANSITIONS
EXCITED STATES
HALIDES
HALOGEN COMPOUNDS
KINETICS
METASTABLE STATES
MOLECULE COLLISIONS
NONMETALS
RARE GAS COMPOUNDS
RARE GASES
REACTION KINETICS
SPECTRA
XENON
XENON CHLORIDES
XENON COMPOUNDS