Photodissociation dynamics of methylamine in the blue edge of the A-band. II. The NH2 + CH3 channel

The photodissociation dynamics leading to the C-N bond cleavage in methylamine (CH3NH2) are investigated upon photoexcitation in the blue edge of the first absorption A-band, in the 198-204 nm range. Velocity map images of the generated methyl (CH3) fragment detected in specific vibrational modes, i.e., nu = 0,. nu(1) = 1, and nu(2) = 1, through resonance enhanced multiphoton ionization, are presented along with the corresponding translational energy distributions and the angular analysis. The experimental results are complemented by high-level ab initio calculations of potential energy curves as a function of the C-N bond distance. While a similar single Boltzmann-type contribution is observed in all the translational energy distributions measured, the speed-dependent anisotropy parameter obtained through the angular analysis reveals the presence of two different mechanisms. Prompt dissociation through the conical intersection between the (A) over tilde (1)A' first excited state and the ground state located in the exit channel is, indeed, revealed as a minor channel. In contrast, slow dissociation on the ground state, presumably from frustrated N-H bond cleavage trajectories, constitutes the major reaction pathway leading to the methyl formation.

Automated summary

The photodissociation dynamics of methylamine (CH3NH2) upon photoexcitation in the blue edge of the first absorption A-band are studied. The velocity map images of methyl (CH3) fragment and corresponding translational energy distributions and angular analysis are presented. The results show two different mechanisms: prompt dissociation through conical intersection and slow dissociation on the ground state.