Photodissociation Dynamics and Stereodynamics of Methyl Mercaptan and Dimethyl Sulfide from the Second Absorption Band at 201 and 210 nm.

The role of promoting and spectator modes vs energy randomization in nonadiabatic dynamics is interrogated in the photodissociation of methyl mercaptan, CHSH, and dimethyl sulfide, CHSCH or DMS, in the second absorption band. The primary CH(ν) radicals produced in the dissociation of both systems at 210 nm have been resonantly detected in slice-imaging experiments, and the corresponding translational energy and angular distributions have been obtained. The stereodynamical information provided by Dixon's bipolar moments in conjunction with the energy partitioning among the different degrees of freedom of the primary CH(ν) products offers a panoramic picture of the photodissociation process of both systems. The remarkable similitude found between the two systems related to both vector correlations and internal energy content of the corresponding counterparts-SH for methyl mercaptan and SCH for DMS-indicates that despite the diabaticity of the process, no efficient energy randomization of the available energy takes place. More specifically, only the parent vibrational modes whose participation in the initial absorption step is imposed by the conical intersection-i.e., the promoting modes-are adiabatically preserved during the process, while the rest of the vibrational modes play the spectator role. The results for both molecules at 210 nm are complemented with experiments carried out for DMS at 201 nm to explore the internal mechanism of the conical intersection in different zones of the absorption region.