Deactivation rate constants and product branching in collisions of the Xe(6p) states with Kr and Ar

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Abstract
The quenching kinetics of the Xe(6p[1/2]0 ), Xe(6p[3/2]2 ), and Xe(6p[5/2]2 ) states have been studied in Kr and Ar buffer gas at room temperature using the two‐photon, laser‐excitation technique. The total quenching rate constants and the primary product distributions were measured to obtain state‐to‐state rate constants. Collisions between Xe[1/2]0 and Kr mainly gave energy transfer to Kr(5s,3P2 ) rather than relaxation to the Xe(6p or 5d) levels. The transfer of energy from Kr(5s,3P2 ) back to the Xe(6p) manifold also was observed. The collisional coupling between Xe[1/2]0 and Xe(3d5 ) in Ar, reported previously, was confirmed. The collisions of Kr and Ar with Xe[3/2]2 and Xe[5/2]2 atoms gave intramultiplet relaxation; observation of the time dependence of the primary products, the Xe[3/2]1, [5/2]3, and [1/2]1 states, permitted assignment of some state‐to‐state rate constants for these states. The flow of energy through the Xe(6p) manifold is discussed.