Product Branching in the Low Temperature Reaction of CN with Propyne by Chirped-Pulse Microwave Spectroscopy in a Uniform Supersonic Flow
Name
Field_Product branching.pdf
Size
1.18 MB
Format
Adobe PDF
Checksum (MD5)
cf31d8b9118cf03b737ac9118d09c8c0
Author(s)
Abeysekera, Chamara
Joalland, Baptiste
Ariyasingha, Nuwandi
Zack, Lindsay N.
Sims, Ian R.
Suits, Arthur G.
Field, Robert W
Date Issued
April 2015
Journal
Journal of Physical Chemistry Letters
Publisher
American Chemical Society (ACS)
Citation
Abeysekera, Chamara, Baptiste Joalland, Nuwandi Ariyasingha, Lindsay N. Zack, Ian R. Sims, Robert W. Field, and Arthur G. Suits. "Product Branching in the Low Temperature Reaction of CN with Propyne by Chirped-Pulse Microwave Spectroscopy in a Uniform Supersonic Flow." Journal of Physical Chemistry Letters 6:9 (2015), pp. 1599-1604. © 2015 American Chemical Society.
Version
Final published version
Abstract
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 + 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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
Terms of Use
Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
Persistent DSpace Link
DOI of Published Version
https://doi.org/10.1021/acs.jpclett.5b00519
