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

Leavitt, Christopher M.; Moradi, Christopher P.; Acrey, Bradley W.; Douberly, Gary E.

doi:10.1063/1.4844175

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

Journal Article · Mon Dec 16 00:00:00 EST 2013 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4844175· OSTI ID:1409050

Leavitt, Christopher M. ^[1]; Moradi, Christopher P. ^[2]; Acrey, Bradley W. ^[2]; ^[2]

Univ. of Georgia, Athens, GA (United States); University of Georgia, Athens, GA
Univ. of Georgia, Athens, GA (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Georgia Research Foundation, Athens, GA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0008086

OSTI ID:: 1409050

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 23 Vol. 139; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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