THE REACTION OF O(P-3) WITH OCLO

The laser photolysis-long path transient absorption technique was used to study the mechanism and products of the reaction O(P-3) + OClO(M)u nder right arrow Products (3) at 260 K in 100 to 400 torr of He, N-2, and Ar. ClO was not detected as a reaction product, < 5% yield, from t his reaction at 400 torr and 260 K. A broad UV absorption feature asso ciated with a product of this reaction, with a peak located at 260 nm, was observed. The peak absorption cross section of this species was m easured to be (1.72 +/- 0.12) X 10-(17) cm(2) molecule(-1). The rate c oefficient for the appearance of this species was measured to be (1.69 +/- 0.46) X 10-(13) cm(3) molecule(-1) s(-1) and was independent of p ressure. The rate coefficient for the appearance of the species is ca. 10 times lower than that for the disappearance of O(P-3), indicating that the observed species is not a direct product of the reaction of O (P-3) with OClO. Mechanistic considerations and the possible identity of the absorber are discussed. (C) 1997 John Wiley & Sons, Inc.