Propensity towards H photofragments in the photodissociation of CD(3)NH(2) pre-excited to the first N-H stretch overtone Academic Article uri icon

abstract

  • Vibrationally mediated photodissociation combined with (2 + 1) resonantly enhanced multiphoton ionization detection of H and D photoproducts was used to assess selective bond fission in partially deuterated methylamine, CD3NH2. Jet-cooled action spectra and Doppler profiles of the H and D photofragments were obtained via ∼243.1 nm photodissociation of the parent containing two quanta of N–H stretch excitation. The multiband action spectra indicate that the energy flow out of the initially prepared N–H stretch to the bath states is on a picosecond time scale and that the 2v 10 state (antisymmetric N–H stretch) is longer lived than the other states. Although the specificity attained by N–H stretch excitation was lost, the photofragment yield of H was nine times higher than that of D, indicating preferential N–H bond fission due to lower transition states on the excited state surface.

publication date

  • January 1, 2008