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Author(s):   Danielache, S.O.; Johnson, M.S.; Nanbu, S.; Grage, M.ML.; McLinden, C.; Yoshida, N.
Title:   Ab initio study of sulfur isotope fractionation in the reaction of OCS with OH
Journal:   Chem. Phys. Lett.
Volume:   450
Page(s):   214 - 220
Year:   2008
Reference type:   Journal article
Squib:   2008DAN/JOH214-220

Reaction:   COS + ·OHCO2 + SH
Reaction order:   2
Temperature:   298 K
Rate expression:   no rate data available
Category:  Theory
Data type:   Ab initio
Comments:   The fractionation of sulfur isotopes in the gas-phase reaction of OCS with OH was calculated by ab initio methods. The first reaction step occurs through a carbon bonded OH–OCS transition state. The activation barrier is 18.4 kJ mol-1 (CCSD(T)/aug-cc-pVDZ level plus zero-point energy) relative to the reactants. Fractionation constants are -1.4, -2.6 and -6.3‰ for 33S, 34S and 36S respectively. These results bring new insight regarding the origin of stratospheric sulfate aerosols, including the identification of characteristic isotopic fractionations in the lower and middle stratosphere.

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