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Understanding the chemical dynamics of the reactions of dicarbon with 1-butyne, 2-butyne, and 1,2-butadiene – toward the formation of resonantly stabilized free radicals

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/c4cp00639a· OSTI ID:1603786
 [1];  [2];  [2];  [2];  [3];  [3]
  1. Univ. of Hawaii at Manoa, Honolulu, HI (United States); University of Hawaii at Manoa
  2. Univ. of Hawaii at Manoa, Honolulu, HI (United States)
  3. Florida International Univ., Miami, FL (United States)
+ Show Author Affiliations

In this work, the reaction dynamics of the dicarbon radical C2(a3Πu/X1Σg+) in the singlet and triplet state with C4H6 isomers 2-butyne, 1-butyne and 1,2-butadiene were investigated at collision energies of about 26 kJ mol-1 using the crossed molecular beam technique and supported by ab initio and RRKM calculations. The reactions are all indirect, forming C6H6 complexes through barrierless additions by dicarbon on the triplet and singlet surfaces. Isomerization of the C6H6 reaction intermediate leads to product formation by hydrogen loss in a dicarbon–hydrogen atom exchange mechanism forming acyclic C6H5 reaction products through loose exit transition states in overall exoergic reactions.

Research Organization:
Univ. of Hawaii, Honolulu, HI (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
FG02-03ER15411; FG02-04ER15570
OSTI ID:
1603786
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 24 Vol. 16; ISSN 1463-9076; ISSN PPCPFQ
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (2)

A combined crossed molecular beams and computational study on the formation of distinct resonantly stabilized C 5 H 3 radicals via chemically activated C 5 H 4 and C 6 H 6 intermediates journal January 2018
On the formation and the isomer specific detection of methylacetylene (CH 3 CCH), propene (CH 3 CHCH 2 ), cyclopropane (c-C 3 H 6 ), vinylacetylene (CH 2 CHCCH), and 1,3-butadiene (CH 2 CHCHCH 2 ) from interstellar methane ice analogues journal January 2019

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