Experimental investigation of the chemistry of excited states of rare gases. Annual technical progress report, October 15, 1976--October 14, 1977

Tunable dye laser fluorescence has been combined with the flowing afterglow technique as a method for studying reactive intermediates present in the flowing afterglow. The radiative lifetimes and two-body quenching rate constants (with Ar carrier gas) for the Ar*(3p5,4p) and Ar*(3p5,5p) excited states were reported in the preceding year. During this year, we have measured the Ar* product states from the two-body quenching. More than 50% of the quenching leads directly to intermultiplet transfer to Ar(4s) states, rather than to intramultiplet cascade down the Ar(4p) manifold. Using this technique we also have studied the Xe(5p5,6p') and Xe(5p5,7p) excited states and radiative lifetimes, two-body quenching and the product states from quenching have been ascertained. These data should be of value for modeling energy flow pathways of rare gases excited by high energy electrons. A method has been developed for studying the quenching of the XeF(B) and KrF(B) by a variety of reagent molecules. A preliminary account of this work was published (number 5 in the publication list). Much additional experimental work has been done and a definitive study of the electronic quenching of XeF(B) and KrF(B) is in progress. Efforts to interpret (and publish) our comprehensive studies of the reactive quenching of the Kr(3P2) and Xe(3P2) by fluorine and chlorine-containing molecules has continued (see numbers 4, 6 and 8 in the publication listing). Two more manuscripts are in final stages of preparation. Of particular importance has been the development of methods for simulating and interpreting the bound-free emission spectra from the very high vibrational levels of the xenon and krypton fluorides and chlorides. Experiments have been done to measure the branching ratios for (i) ArF* formation from reactive quenching of Ar(3P2) with fluorine-containing reagents and (ii) KrBr* and Br* formation for Kr(3P2) reacting with some bromine-containing molecules