Photoexcitation spectra of transition region species in reactions of potassium with sodium halides

Barnes, Michael D.; Brooks, Philip R.; Curl, R. F.; Harland, Peter W.; Johnson, Bruce R.
March 1992
Journal of Chemical Physics;3/1/1992, Vol. 96 Issue 5, p3559
Academic Journal
Emission at 589.0 nm from Na atoms is observed when beams of K and NaX (X=Cl, Br, I) are crossed inside the cavity of a cw dye laser tuned to wavelengths not resonant with either the isolated reagents or products. This emission is interpreted as the signature of light absorption by a system in the process of chemical reaction, and the variation of this emission intensity with probe wavelengths is an excitation spectrum of ‘‘transition region species’’ formed in these reactions. Each spectrum displays a ‘‘blue’’ feature where the emission intensity increases sharply as the probe wavelength approaches the Na D lines. A second ‘‘red’’ feature is also observed in all of the spectra. This feature appears as a well resolved maximum for the Br and I systems peaked at ∼610 nm, and is much broader for the Cl system with the maximum at ∼640 nm. Definitive assignment of these features is not yet possible, but several possible mechanisms are proposed which may give insight into the reaction dynamics.


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