jz5b00519_si_001.pdf (339.12 kB)
Product Branching in the Low Temperature Reaction of CN with Propyne by Chirped-Pulse Microwave Spectroscopy in a Uniform Supersonic Flow
journal contribution
posted on 2015-12-17, 08:07 authored by Chamara Abeysekera, Baptiste Joalland, Nuwandi Ariyasingha, Lindsay
N. Zack, Ian R. Sims, Robert W. Field, Arthur G. SuitsA 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 + CH3CCH
reaction was found to yield HCN via a direct H-abstraction reaction,
whereas indirect addition/elimination pathways to HCCCN, CH3CCCN, and CH2CCHCN 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, CH3CCCN,
and CH2CCHCN, 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.