On the Dynamics of Xylene Isomers Excited in the Vacuum-Ultraviolet (VUV) Region.

We report on the dynamics of electronically excited o-, m-, and p-xylene on the femtosecond timescale by employing the vacuum-ultraviolet pump-IR probe mass spectrometry technique. The molecules were excited by the fifth harmonic (λ=160 nm) of a Ti:sapphire laser at a superposition of the S3 valence with several Rydberg states. The relaxation pathways were investigated by studying the parent P(+) and the fragment [P-H](+) and [P-CH3 ](+) time-resolved signals generated after interaction with the fundamental beam (λ=800 nm). Relaxation from the excited valence states was found to depend on the relative positions of the methyl groups on the ring. An increasing trend in the order ovalence state S2 presented the opposite trend. Conclusions on the possible deformations and vibrations induced during the relaxation process were drawn: ring deformation involving methyl motion takes place.