Kinetics of the vibrational deactivation of OH X2II (=3, 2, 1) with hydrides and reduced sulfides

Abstract

The deactivation kinetics of vibrationally excited OH X 2 II were studied using the pulsed laser photolysis–pulsed laser induced fluorescence technique. Photolysis of O 3 at 266 nm was used to produce O( 1 D) which reacted rapidly with a precursor to produce OH(v). Temporal profiles of OH(v) were obtained by exciting off-diagonal (Δv = −1) transitions in the A–X band of OH and monitoring the diagonal, blue-shifted fluorescence. Deactivation rate coefficients for OH (v = 3, 2, 1) with H 2 O and CH 4 and for OH (v = 2, 1) with NH 3 , CS 2 , (CH 3 ) 2 S, CH 3 SH and CH 3 Br were obtained. The mechanisms of deactivation and the relationship of the deactivation rate coefficients to the thermal association rate coefficients for OH complexes are discussed.