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Issue 44, 2008
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Rotationally resolved infrared spectroscopy of a jet-cooled phenyl radical in the gas phase

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Abstract

The first high-resolution IR spectra of a jet-cooled phenyl radical are reported, obtained via direct absorption laser spectroscopy in a slit-jet discharge supersonic expansion. The observed A-type band arises from fundamental excitation of the out-of-phase symmetric CH stretch mode (ν19) of b2 symmetry. Unambiguous spectral assignment of the rotational structure to the phenyl radical is facilitated by comparison with precision 2-line combination differences from Fourier transform microwave and direct absorption mm-wave measurements on the ground state [R. J. McMahon et al., Astrophys. J., 2003, 590, L61]. Least-squares fits to an asymmetric top Hamiltonian permit the upper-state rotational constants to be obtained. The corresponding gas-phase vibrational band origin at 3071.8904 (10) cm−1 is in remarkably good agreement with previous matrix isolation studies [A. V. Friderichsen et al., J. Am. Chem. Soc., 2001, 123, 1977], and indicates only a relatively minor red shift (≈0.9 cm−1) between the gas and Ar matrix phase environment. Such studies offer considerable promise for further high resolution IR study of other aromatic radical species of particular relevance to combustion phenomena and interstellar chemistry.

Graphical abstract: Rotationally resolved infrared spectroscopy of a jet-cooled phenyl radical in the gas phase

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Publication details

The article was received on 01 Aug 2008, accepted on 19 Aug 2008 and first published on 03 Oct 2008


Article type: Communication
DOI: 10.1039/B813256A
Citation: Phys. Chem. Chem. Phys., 2008,10, 6592-6596
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    Rotationally resolved infrared spectroscopy of a jet-cooled phenyl radical in the gas phase

    E. N. Sharp, M. A. Roberts and D. J. Nesbitt, Phys. Chem. Chem. Phys., 2008, 10, 6592
    DOI: 10.1039/B813256A

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