Spectroscopic Studies of the Products of the Reactions of Excited Noble-Gas Atoms.
Final scientific rept. 15 Mar 79-14 May 83,
PITTSBURGH UNIV PA DEPT OF CHEMISTRY
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The products of the very rapid reactions of electronically-excited Ar, Kr and Xe atoms with several oxygen-, hydrogen- and halogen-containing compounds have been investigated using the saturation ion-current technique and emission and atomic resonance fluorescence spectroscopy in discharge-flow systems. New insight has been obtained into the mechanisms of the channels leading to chemiionization and noble-gas halide formation. Energy transfer leading to molecular dissociation is the major and often the dominant channel, with one or more atoms being eliminated in strong preference to elimination of molecular or electronically-excited fragments. For the excited noble gas atoms, the high quenching efficiency and dominance of dissociation and ionization channels are associated with the availability of accessible acceptor states of the quenching molecule, as revealed by its absorption spectrum. It is proposed that these efficient reactions occur by energy transfer at relatively long range with no major prior distortion of the quenching molecule. It is expected that this model should be directly applicable to the reactions of certain other excited species, which exhibit a similar correlation of quenching rate constants with the availability of acceptor states at the appropriate energy. Author
- Inorganic Chemistry
- Atomic and Molecular Physics and Spectroscopy