Infrared diode laser spectroscopy of the allyl radical. The ν11 band
- 1 September 1992
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 97 (5) , 2963-2970
- https://doi.org/10.1063/1.463037
Abstract
Allyl radicals were generated by the photolysis of 1,5‐hexadiene at 193 nm and were detected by observing the ν11, i.e., CH2 symmetric wagging band by infrared diode laser kinetic spectroscopy. The observed spectrum showed clearly the effect of nuclear‐spin statistical weights, establishing the presence of a Cb2 axis in the molecule. The spin–rotation splitting was not resolved; only some high‐Ka lines were found broader than others, placing an upper limit for the εaa constant at about 200 MHz or less. The rotational constants derived from the observed spectrum indicate that the molecule is essentially planar. The C–C bond length and the CCC bond angle were calculated from the ground‐state rotational constants to be 1.3869 Å and 123.96°, respectively, where structural parameters involving hydrogens were fixed to those of ab initio values.Keywords
This publication has 34 references indexed in Scilit:
- Ab initio quantum mechanical calculation of vibrational frequencies, infrared intensities and equilibrium geometry of the allyl radicalSpectrochimica Acta Part A: Molecular Spectroscopy, 1990
- An a b i n i t i o study of the structure and vibrational spectra of allyl and 1,4-pentadienyl radicalsThe Journal of Chemical Physics, 1990
- Photochemical electrocyclization of the allyl radical into the cyclopropyl radicalJournal of Physical Organic Chemistry, 1990
- A theoretical investigation of the thermal ring opening of cyclopropyl radical into allyl radical. Evidence for a highly nonsymmetric transition stateJournal of the American Chemical Society, 1990
- Carbon-13 hyperfine constants of allyl radicalThe Journal of Physical Chemistry, 1988
- Electronic Energy Levels of Small Polyatomic Transient MoleculesJournal of Physical and Chemical Reference Data, 1988
- Observation of the 3s 2A1 Rydberg states of allyl and 2-methylallyl radicals with multiphoton ionization spectroscopyThe Journal of Physical Chemistry, 1985
- Electronic spectra of the free allyl radical and some of its simple derivativesTransactions of the Faraday Society, 1968
- The Electronic Mechanism of Electrocyclic ReactionsJournal of the American Chemical Society, 1965
- REACTIONS OF ALLYL ALCOHOL-1-C14Journal of the American Chemical Society, 1953