Reactions O(³P, ¹D) + HCCCN(X¹S⁺) (Cyanoacetylene): Crossed-Beam and Theoretical Studies and Implications for the Chemistry of Extraterrestrial Environments

Cyanoacetylene (HCCCN), the first member of the cyanopolyyne family (HCnN, where n = 3, 5, 7, ...), is of particular interest in astrochemistry being ubiquitous in space (molecular envelopes, and external galaxies) and also relatively abundant. It is also abundant in the upper atmosphere of Titan and comets. Since oxygen is the third most abundant element in space, after hydrogen and helium, the reaction O + HCCCN can be of relevance in the chemistry of extraterrestrial environments. Despite that, scarce information exists not only on the reactions of oxygen atoms with cyanoacetylene but with nitriles in general. Here, we report on a combined experimental and theoretical investigation of the reactions of cyanoacetylene with both ground P-3 and excited 1D atomic oxygen and provide detailed information on the primary reaction products, their branching fractions (BFs), and the overall reaction mechanisms. More specifically, the reactions of O(P-3, D-1) with HCCCN(X-1 sigma(+)) have been investigated under single-collision conditions by the crossed molecular beams scattering method with mass spectrometric detection and time-of-flight analysis at the collision energy, E-c,E- of 31.1 kJ/mol. From product angular and time-of-flight distributions, we have identified the primary reaction products and determined their branching fractions (BFs). Theoretical calculations of the relevant triplet and singlet potential energy surfaces (PESs) were performed to assist the interpretation of the experimental results and clarify the reaction mechanism. Adiabatic statistical calculations of product BFs for the decomposition of the main triplet and singlet intermediates have also been carried out. Merging together the experimental and theoretical results, we conclude that the O(P-3) reaction is characterized by a minor adiabatic channel leading to OCCCN (cyanoketyl) + H (experimental BF = 0.10 +/- 0.05), while the dominant channel (BF = 0.90 +/- 0.05) occurs via intersystem crossing to the underlying singlet PES and leads to formation of (HCCN)-H-1 (cyanomethylene) + CO. The O(D-1) reaction is characterized by the same two channels, with the relative CO/H yield being slightly larger. Considering the recorded reactive signal and the calculated entrance barrier, we estimate that the rate coefficient for reaction O(3P) + HC3N at 300 K is in the 10(-12) cm(3) molec(-1 )s(-1) range. Our results are expected to be useful to improve astrochemical and photochemical models. In addition, they are also relevant in combustion chemistry, because the thermal decomposition of pyrrolic and pyridinic structures present in fuel-bound nitrogen generates many nitrogen-bearing compounds, including cyanoacetylene.