Spectroscopy of the transition state. II. F+Na2→FNaNa‡*→NaF+Na*

Abstract

Chemiluminescence from the reaction F+Na₂→NaF+Na* (3 ²P) has been studied in crossed uncollimated beams at a reagent pressure of ∼10⁻⁵ Torr, with systematic variation of experimental conditions. The atomic D line emission is accompanied by ‘‘wing’’ emission extending over several hundred angstroms, to either side of the D line. The source of the wing emission has been examined in some detail. The earlier proposal [J. Chem. Phys. 73, 5895 (1980)] that the wing comprises the emission spectrum of transition states FNaNa^‡* which exist as the reaction products are in the process of separating, is in best accord with the observations. The kinetics, spectral shape, and intensity of the wings provide the principal clues as to their origin. The red and blue wings differ in shape. The integrated intensity in the red is approximately twice that in the blue. Alternative models are considered.