Jump to main content
Jump to site search


REACTION MECHANISM AND PRODUCT BRANCHING RATIOS OF THE CH + C3H4 REACTIONS: A THEORETICAL STUDY

Abstract

Two ground state CH radical reactions with C3H4 isomers allene and methylacetylene occurring along the C4H5 potential energy surface (PES) have been studied in order to probe the reaction mechanisms and final product distributions. The calculations have been performed using a CCSD(T)-F12//B2PLYPD3 PES in combination with the 1-D chemical master equation. The reaction between the CH radical and allene was found to lead to exclusive “funneling” of the energized C4H5 intermediates into the linear C4H5 configurations prior reaching the exit channels, regardless of the specific nature of the initial bimolecular reactive encounter. In the case of the CH radical reaction with methylacetylene, energized C4H5 three-membered ring structures undergo H loss in significant amounts resulting in the production of the cyclic C4H4 methylenecyclopropene product, in accordance with experiments. The theoretical product distribution at room temperature for methylacetylene + CH is ~35% methylenecyclopropene, ~36% vinylacetylene, and ~28% 1,2,3-butatriene, which is in agreement with available experimental data. The distribution for allene + CH is ~93% vinylacetylene, ~4% 1,2,3-butatriene and ~3% acetylene + vinyl, which overestimates the experimental yield of vinylacetylene and underestimates that of 1,2,3-butatriene by ~10%. Possible reasons for this slight quantitative deviation of the theoretical results obtained within statistical treatment from experiment have been discussed.

Back to tab navigation
Please wait while Download options loads

Supplementary files

Publication details

The article was received on 23 Mar 2017, accepted on 03 May 2017 and first published on 05 May 2017


Article type: Paper
DOI: 10.1039/C7CP01873H
Citation: Phys. Chem. Chem. Phys., 2017, Accepted Manuscript
  •   Request permissions

    REACTION MECHANISM AND PRODUCT BRANCHING RATIOS OF THE CH + C3H4 REACTIONS: A THEORETICAL STUDY

    J. M. L. Ribeiro and A. Mebel, Phys. Chem. Chem. Phys., 2017, Accepted Manuscript , DOI: 10.1039/C7CP01873H

Search articles by author