The Reaction N(D) + CHCCH (Methylacetylene): A Combined Crossed Molecular Beams and Theoretical Investigation and Implications for the Atmosphere of Titan.

The reaction of excited nitrogen atoms N(D) with CHCCH (methylacetylene) was investigated under single-collision conditions by the crossed molecular beams (CMB) scattering method with mass spectrometric detection and time-of-flight analysis at the collision energy () of 31.0 kJ/mol. Synergistic electronic structure calculations of the doublet potential energy surface (PES) were performed to assist the interpretation of the experimental results and characterize the overall reaction micromechanism. Theoretically, the reaction is found to proceed via a barrierless of N(D) to the carbon-carbon triple bond of CHCCH and an of N(D) into the CH bond of the methyl group, followed by the formation of cyclic and linear intermediates that can undergo H, CH, and CH elimination or isomerize to other intermediates before unimolecularly decaying to a variety of products. Kinetic calculations for addition and insertion mechanisms and statistical (Rice-Ramsperger-Kassel-Marcus) computations of product branching fractions (BFs) on the theoretical PES were performed at different values of total energy, including the one corresponding to the temperature (175 K) of Titan's stratosphere and that of the CMB experiment. Up to 14 competing product channels were statistically predicted, with the main ones, at = 31.0 kJ/mol, being the formation of CHNH (methanimine) + CH (ethylidyne) (BF = 0.41), -C(N)CH + CH (BF = 0.32), CHCHCN (acrylonitrile) + H (BF = 0.12), and -CHC(N)CH + H (BF = 0.04). Of the 14 possible channels, seven correspond to H displacement channels of different exothermicity, for a total H channel BF of ∼0.25 at = 31.0 kJ/mol. Experimentally, dynamical information could only be obtained about the overall H channels. In particular, the experiment corroborates the formation of acrylonitrile + H, which is the most exothermic of all 14 reaction channels and is theoretically calculated to be the dominant H-forming channel (BF = 0.12). The products containing a novel C-N bond could be potential precursors to form other nitriles (CN, CN) or more complex organic species containing N atoms in planetary atmospheres, such as those of Titan and Pluto. Overall, the results are expected to have a potentially significant impact on the understanding of the gas-phase chemistry of Titan's atmosphere and the modeling of that atmosphere.