Experimental and theoretical investigation of rate coefficients of the reaction S(P-3)+OCS in the temperature range of 298-985 K

Abstract

The reaction S(P-3)+OCS in Ar was investigated over the pressure range of 50-710 Torr and the temperature range of 298-985 K with the laser photolysis technique. S atoms were generated by photolysis of OCS with light at 248 nm from a KrF excimer laser; their concentration was monitored via resonance fluorescence excited by atomic emission of S produced from microwave-discharged SO2. At pressures less than 250 Torr, our measurements give k(298 K)=(2.7 +/- 0.5)x10(-15) cm(3) molecule(-1) s(-1), in satisfactory agreement with a previous report by Klemm and Davis [J. Phys. Chem. 78, 1137 (1974)]. New data determined for 407-985 K connect rate coefficients reported previously for T >= 860 and T <= 478 K and show a non-Arrhenius behavior. Combining our results with data reported at high temperatures, we derived an expression k(T)=(6.1 +/- 0.3)x10(-18) T-1.97 +/- 0.24 exp[-(1560 +/- 170)/T] cm(3) molecule(-1) s(-1) for 298 <= T/K <= 1680. At 298 K and P >= 500 Torr, the reaction rate was enhanced. Theoretical calculations at the G2M(CC2) level, using geometries optimized with the B3LYP/6-311+G(3df) method, yield energies of transition states and products relative to those of the reactants. Rate coefficients predicted with multichannel Rice-Ramsperger-Kassel-Marcus (RRKM) calculations agree satisfactorily with experimental observations. According to our calculations, the singlet channel involving formation of SSCO followed by direct dissociation into S-2(a (1)Delta(g))+CO dominates below 2000 K; SSCO is formed via intersystem crossing from the triplet surface. At low temperature and under high pressure the stabilization of OCS2, formed via isomerization of SSCO, becomes important; its formation and further reaction with S atoms partially account for the observed increase in the rate coefficient under such conditions. (c) 2006 American Institute of Physics.