High level ab initio and density functional theory study of bond selective dissociation of CH3SH and CH3CH2SH radical cations

Selective bond dissociation energies for CH3SH and CH3CH2SH radical cations were evaluated with G1, G2, G2MP2, B3LYP, BLYP, and SVWN computational methods. It was determined that both G2 and CBSQ evaluate very accurate bond dissociation energies for thiol radical cations, while gradient-corrected BLYP computes the best energies of three employed DFT methods. For the CH3CH2SH radical cation, new, higher than previously estimated selective bond dissociation energies were suggested.