Abstract
We report ultraviolet resonance Raman spectra of bromoform (CHBr3) in cyclohexane solution. The resonance Raman spectra show significant intensity in the overtones of the nominal Br-C-Br symmetric bend (v 6), the nominal H-C-Br asymmetric bend (v3), the nominal Br-C-Br symmetric stretch (v 2) and the nominal Br-C-Br asymmetric stretch (v 5) vibrational modes suggesting that the short-time photodissociation dynamics have noticeable multidimensional character. The lack of strong combination bands between several of the Franck-Condon active modes suggests that more than one electronic transition contribute to the resonance Raman spectra. We briefly discuss the ultraviolet short-time photodissociation dynamics of bromoform and the potential implications for the secondary photodissociation reactions of the initially formed CHBr2 radical.