Reaction N(D) + CHCCH (Allene): An Experimental and Theoretical Investigation and Implications for the Photochemical Models of Titan.

We report on a combined experimental and theoretical investigation of the N(D) + CHCCH (allene) reaction of relevance in the atmospheric chemistry of Titan. Experimentally, the reaction was investigated (i) 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 33 kJ/mol to determine the primary products and the reaction micromechanism and (ii) in a continuous supersonic flow reactor to determine the rate constant as a function of temperature from 50 to 296 K. Theoretically, electronic structure calculations of the doublet CHN potential energy surface (PES) were performed to assist the interpretation of the experimental results and characterize the overall reaction mechanism. The reaction is found to proceed via barrierless addition of N(D) to one of the two equivalent carbon-carbon double bonds of CHCCH, followed by the formation of several cyclic and linear isomeric CHN intermediates that can undergo unimolecular decomposition to bimolecular products with elimination of H, CH, HCN, HNC, and CN. The kinetic experiments confirm the barrierless nature of the reaction through the measurement of rate constants close to the gas-kinetic rate at all temperatures. Statistical estimates of product branching fractions (BFs) on the theoretical PES were carried out under the conditions of the CMB experiments at room temperature and at temperatures (94 and 175 K) relevant for Titan. Up to 14 competing product channels were statistically predicted with the main ones at = 33 kJ/mol being formation of -CHC(N)CH + H (BF = 87.0%) followed by CHCCHNH + H (BF = 10.5%) and CHCCNH + H (BF = 1.4%) the other 11 possible channels being negligible (BFs ranging from 0 to 0.5%). BFs under the other conditions are essentially unchanged. Experimental dynamical information could only be obtained on the overall H-displacement channel, while other possible channels could not be confirmed within the sensitivity of the method. This is also in line with theoretical predictions as the other possible channels are predicted to be negligible, including the HCN/HNC + CH (vinyl) channels (overall BF < 1%). The dynamics and product distributions are dramatically different with respect to those observed in the isomeric reaction N(D) + CHCCH (propyne), where at a similar the main product channels are CHNH (methanimine) + CH (BF = 41%), c-C(N)CH + CH (BF = 32%), and CHCHCN (vinyl cyanide) + H (BF = 12%). Rate coefficients (the recommended value is 1.7 (±0.2) × 10 cm s over the 50-300 K range) and BFs have been used in a photochemical model of Titan's atmosphere to simulate the effect of the title reaction on the species abundance (including any new products formed) as a function of the altitude.