Site-dependent photodissociation of vibronically excited CD3NH2 molecules Academic Article uri icon

abstract

  • The mechanism of H and D atom loss, following ultraviolet photolysis of methylamine- d 3 d , CD 3 NH 2 CD , has been studied via electronic action and Doppler spectroscopies. The N–H bond is preferentially cleaved and the yield of both H and D photofragments increases gradually, but differently, as higher vibrational states on the first excited electronic state, A ̃ A , are accessed, leading to some drop in H/D branching ratios. The average translational energies of the H photofragments are somewhat higher than those of D, implying lower energy content left in the internal degrees of freedom of the CD 3 NH CD than in the CD 2 NH 2 CD partner fragment. These results provide evidence for discrimination between the two channels and mechanistic insight into the N–H and C–D bond cleavage.

publication date

  • January 1, 2010