Unsaturated Dinitriles Formation Routes in Extraterrestrial Environments: A Combined Experimental and Theoretical Investigation of the Reaction between Cyano Radicals and Cyanoethene (C2H3CN)

The reaction between cyano radicals (CN, X2Σ+) and cyanoethene (C2H3CN) has been investigated by a combined approach coupling crossed molecular beam (CMB) experiments with mass spectrometric detection and time-of-flight analysis at a collision energy of 44.6 kJ mol–1 and electronic structure calculations to determine the relevant potential energy surface. The experimental results can be interpreted by assuming the occurrence of a dominant reaction pathway leading to the two but-2-enedinitrile (1,2-dicyanothene) isomers (E- and Z-NC–CHCH–CN) in a H-displacement channel and, to a much minor extent, to 1,1-dicyanoethene, CH2C­(CN)2. In order to derive the product branching ratios under the conditions of the CMB experiments and at colder temperatures, including those relevant to Titan and to cold interstellar clouds, we have carried out RRKM statistical calculations using the relevant potential energy surface of the investigated reaction. We have also estimated the rate coefficient at very low temperatures by employing a semiempirical method for the treatment of long-range interactions. The reaction has been found to be barrierless and fast also under the low temperature conditions of cold interstellar clouds and the atmosphere of Titan. Astrophysical implications and comparison with literature data are also presented. On the basis of the present work, 1,2-dicyanothene and 1,1-dicyanothene are excellent candidates for the search of dinitriles in the interstellar medium.