Display options
Cite
Buckingham GT, Chang CH, Nesbitt DJ. High-resolution rovibrational spectroscopy of jet-cooled phenyl radical: the ν19 out-of-phase symmetric CH stretch. J Phys Chem A. 2013;117(39):10047-57doi: 10.1021/jp400702p.
Buckingham, G. T., Chang, C. H., & Nesbitt, D. J. (2013). High-resolution rovibrational spectroscopy of jet-cooled phenyl radical: the ν19 out-of-phase symmetric CH stretch. The journal of physical chemistry. A, 117(39), 10047-57. https://doi.org/10.1021/jp400702p
Buckingham, Grant T, et al. "High-resolution rovibrational spectroscopy of jet-cooled phenyl radical: the ν19 out-of-phase symmetric CH stretch." The journal of physical chemistry. A vol. 117,39 (2013): 10047-57. doi: https://doi.org/10.1021/jp400702p
Buckingham GT, Chang CH, Nesbitt DJ. High-resolution rovibrational spectroscopy of jet-cooled phenyl radical: the ν19 out-of-phase symmetric CH stretch. J Phys Chem A. 2013 Oct 03;117(39):10047-57. doi: 10.1021/jp400702p. Epub 2013 Apr 17. PMID: 23537501.
Copy Download .nbib Format: NLM
Share it on

J Phys Chem A. 2013 Oct 03;117(39):10047-57. doi: 10.1021/jp400702p. Epub 2013 Apr 17.

High-resolution rovibrational spectroscopy of jet-cooled phenyl radical: the ν19 out-of-phase symmetric CH stretch.

The journal of physical chemistry. A

Grant T Buckingham, Chih-Hsuan Chang, David J Nesbitt

Affiliations

  1. JILA, National Institute of Standards and Technology and Department of Chemistry and Biochemistry, University of Colorado , Boulder, Colorado 80309, United States.

PMID: 23537501 DOI: 10.1021/jp400702p

Abstract

Phenyl radical has been studied via sub-Doppler infrared spectroscopy in a slit supersonic discharge expansion source, with assignments for the highest frequency b2 out-of-phase C-H symmetric stretch vibration (ν19) unambiguously confirmed by ≤6 MHz (0.0002 cm(-1)) agreement with microwave ground state combination differences of McMahon et al. [Astrophys. J. 2003, 590, L61-64]. Least squares analysis of over 100 resolved rovibrational peaks in the sub-Doppler spectrum to a Watson Hamiltonian yields precision excited-state rotational constants and a vibrational band origin (ν0 = 3071.8915(4) cm(-1)) consistent with a surprisingly small red-shift (0.9 cm(-1)) with respect to Ar matrix isolation studies of Ellison and co-workers [J. Am. Chem. Soc. 2001, 123, 1977]. Nuclear spin weights and inertial defects confirm the vibrationally averaged planarity and (2)A1 rovibronic symmetry of phenyl radical, with analysis of the rotational constants consistent with a modest C2v distortion of the carbon backbone frame due to partial sp rehybridization of the σ C radical-center. Most importantly, despite the number of atoms (N = 11) and vibrational modes (3N - 6 = 27), phenyl radical exhibits a remarkably clean jet cooled high-resolution IR spectrum that shows no evidence of intramolecular vibrational relaxation (IVR) phenomena such as local or nonlocal perturbations due to strongly coupled nearby dark states. This provides strong support for the feasibility of high-resolution infrared spectroscopy in other aromatic hydrocarbon radical systems.

Publication Types