Gas-Phase Formation and Isomerization Reactions of Cyanoacetaldehyde, a Prebiotic Molecule of Astrochemical Interest

Cyanoacetaldehyde (NC–CH₂CHO) is considered, together with guanidine and urea, as a precursor of the pyrimidine bases cytosine and uracil. Although it has not yet been detected in the interstellar medium (ISM), several hypotheses have been put forward about its synthesis in solution and in the gas phase. In this paper, we present a gas-phase model of the barrierless reaction between formyl (HCO) and cyanomethyl (CH₂CN) radicals leading to cyanoacetaldehyde and focus on its evolution through isomerization and dissociation pathways. The potential-energy surface for all reactions has been explored by DFT calculations employing double-hybrid functionals and further refined through the “Cheap” composite scheme. Our results indicate that the direct association of the two reacting radicals (HCO and CH₂CN) is strongly exothermic and thus thermodynamically favored under the harsh conditions of the ISM. Microcanonical rate constants computed with the help of the StarRate program for energies up to 6 kJ mol^–1 above the dissociation limit show that the most abundant products are the two conformers of cyanoacetaldehyde (nitrile and carbonyl groups in a cis or trans configuration) which, despite having comparable stability, are obtained with a cis/trans ratio of 0.35:0.65. The formation of other products with relative abundances not exceeding 10% is also discussed.