skip to main content

DOE PAGESDOE PAGES

Title: Infrared laser spectroscopy of the helium-solvated allyl and allyl peroxy radicals

Infrared spectra in the C–H stretch region are reported for the allyl (CH 2CHCH 2) and allyl peroxy (CH 2=CH–CH 2OO·) radicals solvated in superfluid helium nanodroplets. Nine bands in the spectrum of the allyl radical have resolved rotational substructure. We have assigned three of these to the ν 1 (a 1), ν 3 (a 1), and ν 13 (b 2) C–H stretch bands and four others to the ν 14/(ν 15+2ν 11) (b 2) and ν 2/(ν 4+2ν 11) (a 1) Fermi dyads, and an unassigned resonant polyad is observed in the vicinity of the ν 1 band. Experimental coupling constants associated with Fermi dyads are consistent with quartic force constants obtained from density functional theory computations. The peroxy radical was formed within the He droplet via the reaction between allyl and O 2 following the sequential pick-up of the reactants. Five stable conformers are predicted for the allyl peroxy radical, and a computed two-dimensional potential surface for rotation about the CC–OO and CC–CO bonds reveals multiple isomerization barriers greater than ≈300 cm –1. Furthermore, the C–H stretch infrared spectrum is consistent with the presence of a single conformer following the allyl + O 2 reaction within helium droplets.
Authors:
 [1] ;  [1] ;  [1] ; ORCiD logo [1]
  1. Univ. of Georgia, Athens, GA (United States)
Publication Date:
Grant/Contract Number:
SC0008086
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 139; Journal Issue: 23; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Univ. of Georgia Research Foundation, Athens, GA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1409050

Leavitt, Christopher M., Moradi, Christopher P., Acrey, Bradley W., and Douberly, Gary E.. Infrared laser spectroscopy of the helium-solvated allyl and allyl peroxy radicals. United States: N. p., Web. doi:10.1063/1.4844175.
Leavitt, Christopher M., Moradi, Christopher P., Acrey, Bradley W., & Douberly, Gary E.. Infrared laser spectroscopy of the helium-solvated allyl and allyl peroxy radicals. United States. doi:10.1063/1.4844175.
Leavitt, Christopher M., Moradi, Christopher P., Acrey, Bradley W., and Douberly, Gary E.. 2013. "Infrared laser spectroscopy of the helium-solvated allyl and allyl peroxy radicals". United States. doi:10.1063/1.4844175. https://www.osti.gov/servlets/purl/1409050.
@article{osti_1409050,
title = {Infrared laser spectroscopy of the helium-solvated allyl and allyl peroxy radicals},
author = {Leavitt, Christopher M. and Moradi, Christopher P. and Acrey, Bradley W. and Douberly, Gary E.},
abstractNote = {Infrared spectra in the C–H stretch region are reported for the allyl (CH2CHCH2) and allyl peroxy (CH2=CH–CH2OO·) radicals solvated in superfluid helium nanodroplets. Nine bands in the spectrum of the allyl radical have resolved rotational substructure. We have assigned three of these to the ν1 (a1), ν3 (a1), and ν13 (b2) C–H stretch bands and four others to the ν14/(ν15+2ν11) (b2) and ν2/(ν4+2ν11) (a1) Fermi dyads, and an unassigned resonant polyad is observed in the vicinity of the ν1 band. Experimental coupling constants associated with Fermi dyads are consistent with quartic force constants obtained from density functional theory computations. The peroxy radical was formed within the He droplet via the reaction between allyl and O2 following the sequential pick-up of the reactants. Five stable conformers are predicted for the allyl peroxy radical, and a computed two-dimensional potential surface for rotation about the CC–OO and CC–CO bonds reveals multiple isomerization barriers greater than ≈300 cm–1. Furthermore, the C–H stretch infrared spectrum is consistent with the presence of a single conformer following the allyl + O2 reaction within helium droplets.},
doi = {10.1063/1.4844175},
journal = {Journal of Chemical Physics},
number = 23,
volume = 139,
place = {United States},
year = {2013},
month = {12}
}