Product Branching in the Low Temperature Reaction of CN with Propyne by Chirped-Pulse Microwave Spectroscopy in a Uniform Supersonic Flow

A new chirped-pulse/uniform flow (CPUF) spectrometer has been developed and used to determine product branching in a multichannel reaction. With this technique, bimolecular reactions can be initiated in a cold, thermalized, high-density molecular flow and a broadband microwave spectrum acquired for all products with rotational transitions within a chosen frequency window. In this work, the CN + CH<sub>3</sub>CCH reaction was found to yield HCN via a direct H-abstraction reaction, whereas indirect addition/elimination pathways to HCCCN, CH<sub>3</sub>CCCN, and CH<sub>2</sub>CCHCN were also probed. From these observations, quantitative branching ratios were established for all products as 12(5)%, 66(4)%, 22(6)%, and 0(8)% into HCN, HCCCN, CH<sub>3</sub>CCCN, and CH<sub>2</sub>CCHCN, respectively. The values are consistent with statistical calculations based on new ab initio results at the CBS-QB3 level of theory. This work is a demonstration of CPUF as a powerful technique for quantitatively determining the branching into polyatomic products from a bimolecular reaction.