Ultrafast studies of photodissociation in solution: Dissociation, recombination and relaxation

Photodissociation of M(CO){sub 6} (M=Cr,Mo,W) and the formation of solvated M(CO){sub 5}{center_dot}S complex was studied in cyclohexane; rate-limiting step is vibrational energy relaxation from the new bond to the solvent. For both M=Cr and Mo, the primary relaxation occurs in 18 ps; for Cr, there is an additional vibrational relaxation (150 ps time scale) of a CO group poorly coupled to other modes. Relaxation of M=W occurs in 42 ps; several possible mechanisms for the longer cooling are discussed. Vibrational relaxation is also investigated for I{sub 2}{sup -} and IBr{sup {minus}} in nonpolar and slightly polar solvents. Attempts were made to discover the mechanism for the fast energy transfer in nonpolar solvent. The longer time scale dynamics of I{sub 3}{sup {minus}} and IBr{sub 2}{sup {minus}} were also studied; both formed a metastable complex following photodissociation and 90-95% return to ground state in 100 ps, implying a barrier to recombination of 4.3 kcal/mol and a barrier to escape of {ge}5.5 kcal/mol. The more complex photochemistry of M{sub 3}(CO){sub 12} (M=Fe,Ru) is also investigated, using visible and ultraviolet radiations, dissociation, geminate recombination, vibrational relaxation, and bridging structures and their reactions were studied. Attempts were made to extend ultrafast spectroscopy into the mid-infrared, but signal-to-noise was poor