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Journal of Chemical Physics / Volume 133 / Issue 7 / ARTICLES / Gas Phase Dynamics and Structure: Spectroscopy, Molecular Interactions, Scattering, and Photochemistry

J. Chem. Phys. 133, 074304 (2010); http://dx.doi.org/10.1063/1.3469787 (5 pages)

Time- and frequency-resolved photoionization of the C 2A2 state of the benzyl radical, C7H7

Markus Margraf1, Bastian Noller1, Christian Schröter2, Thomas Schultz2, and Ingo Fischer1

1Institute of Physical and Theoretical Chemistry, University of Würzburg, Am Hubland, D-97074 Würzburg, Germany
2Max-Born-Institute, Max-Born-Straße 2a, D-12489 Berlin, Germany

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(Received 12 May 2010; accepted 1 July 2010; published online 17 August 2010)

The structure and dynamics of the C 2A2 electronically excited state of the benzyl radical, C7H7, were investigated by nanosecond and femtosecond pump-probe photoionization. A free jet of benzyl radicals was generated by flash pyrolysis from the precursors 2-phenylethyl nitrite and toluene. Nanosecond multiphoton ionization spectra show a number of vibronic bands that are excited in the wavelength range of 290–310 nm. At excitation wavelengths of 305, 301, and 298 nm, rapid biexponential decay of the excited states was observed. Lifetimes at the C-state origin (305 nm excitation) are 400 fs and 4.5 ps. The lifetimes decrease with increasing excitation energy. The dynamics can be understood within a two-step internal conversion to the electronic ground state.

© 2010 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. EXPERIMENTAL
  3. RESULTS AND DISCUSSION
    1. Mass spectra
    2. Nanosecond REMPI spectrum
    3. Time-resolved traces
  4. SUMMARY AND CONCLUSION

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KEYWORDS and PACS

Keywords

excited states, ground states, molecular configurations, organic compounds, photoionisation, pyrolysis, radiative lifetimes, time resolved spectra, vibronic states

PACS

  • 33.80.Eh

    Autoionization, photoionization, and photodetachment

  • 33.15.Bh

    General molecular conformation and symmetry; stereochemistry

  • 33.70.Ca

    Oscillator and band strengths, lifetimes, transition moments, and Franck-Condon factors

  • 33.20.Wr

    Vibronic, rovibronic, and rotation-electron-spin interactions

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.3469787

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

For access to fully linked references, you need to log in.
    H. -J. Deyerl, I. Fischer, and P. Chen, J. Chem. Phys. 110, 1450 (1999)JCPSA6000110000003001450000001.

    T. Schultz and I. Fischer, J. Chem. Phys. 107, 8197 (1997)JCPSA6000107000019008197000001.

    M. Zierhut, B. Noller, T. Schultz, and I. Fischer, J. Chem. Phys. 122, 094302 (2005)JCPSA6000122000009094302000001.

    F. Negri, G. Orlandi, F. Zerbetto, and M. Zgierski, J. Chem. Phys. 93, 600 (1990)JCPSA6000093000001000600000001.

    D. W. Kohn, H. Clauberg, and P. Chen, Rev. Sci. Instrum. 63, 4003 (1992)RSINAK000063000008004003000001.

    M. Z. Zgierski, S. Patchkovskii, and E. C. Lim, J. Chem. Phys. 123, 081101 (2005)JCPSA6000123000008081101000001.

    H. F. Bettinger, P. R. Schleyer, H. F. Schaefer III, P. R. Schreiner, R. I. Kaiser, and Y. T. Lee, J. Chem. Phys. 113, 4250 (2000)JCPSA6000113000010004250000001.


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