A Study of S( 3 P 2,1,0; 1 D 2 ; 1 S 0 ) Production in the 193 nm Photodissociation of CH 3 SH

The dynamics of S( 3 P 2,1,0; 1 D 2 ; 1 S 0 ) production from the 193 nm photodissociation of CH 3 SH has been examined by 2+1 resonance‐enhanced‐multiphoton‐ionization (REMPI) techniques. Using the rate equation scheme, we have rationalized the intensities of S( 3 P 2,1,0 ; 1 D 2 ; 1 S 0 ) observed according to the sequential two‐photon dissociative pathways, (A): CH 3 SH + hv (193 nm) → CH 3 S + hv (193 nm) → S and (B): CH 3 SH + hv (193 nm) → HS + hv (193 nm) → S, as the major mechanisms for S production. We have satisfactorily fitted the photodissociation laser power dependencies for S( 3 P) and S( 1 D) produced from CH 3 SH by invoking photodissociation cross sections and branching ratios S( 3 P)/S( 1 D) for CH 3 S and HS similar to those determined previously in the 193 nm photodissociation of CH 3 SCH 3 and H 2 S. This observation supports that the 193 nm photodissociation of CH 3 S and HS prepared from CH 3 SH yield predominantly S( l D) and S( 3 P), similar to the cases for CH 3 S prepared from CH 3 SCH 3 and for HS prepared from H 2 S, respectively. A small amount of S( 1 S 0 ) observed from the 193 nm photodissociation of CH 3 SH is attributed to pathway (B).