Theoretical study on the kinetics of the reactions of hydrogen atom, methyl radical with methanethiol and ethanethiol.

An exhaustive and theoretical analysis for the CH3SH + H, CH3SH + CH3·, CH3CH2SH + H and CH3CH2SH + CH3· reactions has been examined using quantum chemistry theory. The potential energy surface was obtained by the CCSD(T)/CBS//M06-2X/cc-pVTZ level of theory. The overall rate coefficients have been analysed and the energetics and reaction enthalpies were also calculated. Three kinds of reaction channels have been analysed: hydrogen abstraction, SH-transfer and CH3-transfer. The calculated kinetics demonstrate that the hydrogen abstraction from the –SH group are major channels at low-temperature region (less than 1000 K). The SH-transfer channels become a competitive reaction channels with the increase in temperature. [ABSTRACT FROM AUTHOR]