The product branching and dynamics of the reaction of chlorine atoms with methylamine

Nascent rotational level population distributions have been measured for the HCl and DCl products of photo-initiated reaction of Cl atoms with CH3NH2, CD3NH2, CH3ND2 and CD3ND2. The use of the different isotopomers of methylamine enables the dynamics of abstraction of H/D atoms from carbon or nitrogen atoms to be distinguished, and the former channel is found to produce HCl or DCl with greater rotational excitation than the latter channel. Mean HCl rotational energies for the two reactions Cl + CH3ND2 → HCl + CH2ND2 and Cl + CD3NH2 → HCl + CD3NH are, respectively, 501 ± 84 and 122 ± 12 cm−1. Fits of the HCl and DCl rotational distributions for reaction of Cl atoms with the CH3NH2 and CD3ND2 molecules with distributions obtained from reactions of the two partially deuterated isotopomers yield branching ratios for C–H ∶ N–H and C–D ∶ N–D abstraction of 0.48 ∶ 0.52 and 0.58 ∶ 0.42, respectively. Ab initio electronic structure theory calculations of the energetics and geometries of transition states and molecular complexes along the reaction pathways for the two competing channels provide key insights to aid the interpretation of the experimental data. The computed bond angle of the N–H–Cl moiety (142.0°) in the transition state for the CH3NH forming channel deviates more from linearity than the C–H–Cl bond angle (171.1°) in the competing transition state, but leads to lower rotational excitation of the nascent HCl products. This counter-intuitive outcome is explained in terms of dipole–dipole interactions between the HCl and organic radical products as they separate