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The analysis of intensity fluctuations for a fully resolved spectrum: Pyrazine

J. Chem. Phys. 88, 6810 (1988); doi:10.1063/1.454379

Issue Date: 1 June 1988

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J. Kommandeur
Laboratory for Physical Chemistry, University of Groningen, 9747 AG Groningen, The Netherlands

W. L. Meerts
Lab. voor Experimentele Natuurkunde, Katholieke Universiteit, Nijmegen, 6525 ED Nijmegen, The Netherlands

Y. M. Engel and R. D. Levine
The Fritz Haber Research Center for Molecular Dynamics, The Hebrew University, Jerusalem 91904, Israel
Intensity fluctuations in the recently published fluorescence excitation spectrum of pyrazine in the 1B3u<--1Ag 0<sup>0</sup><sub>0</sub> band are analyzed. A numerical study of a model Hamiltonian of a bright state coupled to a manifold of dark states is performed as an aid to the interpretation of the results. The distribution of fluctuations in the intensities computed for the model Hamiltonian is near to that expected in the chaotic limit. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 6 November 1987; accepted 11 March 1988
Permalink: http://link.aip.org/link/?JCPSA6/88/6810/1
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KEYWORDS and PACS

Keywords
PACS
  • 33.20.Lg
    Molecular spectra and interactions of molecules with photons Molecular spectra, grouped by wavelength ranges Ultraviolet spectra
  • 33.70.Fd
    Molecular spectra and interactions of molecules with photons Intensities and shapes of molecular spectral lines and bands Lifetimes, absolute and relative line and band intensities
  • 33.50.Dq
    Molecular spectra and interactions of molecules with photons Fluorescence and phosphorescence; radiationless transitions (intersystem crossing, internal conversion) Fluorescence and phosphorescence spectra
  • YEAR: 1988

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

REFERENCES (16)
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  2. E. J. Heller and R. L. Sundberg, in Chaotic Behavior in Quantum Systems, edited by G. Casati (Plenum, New York, 1985).
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  9. The observed [K. K. Lehmann and S. L. Coy, J. Chem. Phys. 83, 3290 (1985) and private communication] intensity fluctuations in NO2 do appear to be near the chaotic limit [J. P. Pique, R. D. Levine, J. L. Kinsey, and R. W. Field (to be published)].
    10. The fluctuations in the fluorescence lifetimes of rovibronic levels in SiH2 [Y. M. Engel, R. D. Levine, J. W. Thoman, J. I. Steinfeld, and R. McKay, J. Chem. Phys. 86, 6561 (1987)] provide the only example of the chaotic limit.
  10. W. M. van Herpen, W. L. Meerts, K. E. Drabe, and J. Kommandeur, J. Chem. Phys. 86, 4396 (1987).
  11. J. Kommandeur, W. A. Majewski, W. L. Meerts, and D. W. Pratt, Annu. Rev. Phys. Chem. 38, 433 (1987).
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  13. K. W. Holtzclaw and D. W. Pratt, Chem. Phys. Lett. 118, 375 (1985).
  14. W. D. Lawrance and A. E. W. Knight, J. Phys. Chem. 89, 917 (1985).
  15. M. Abramowitz and I. A. Stegun, Handbook of Mathematical Functions (Dover, New York, 1965), Chap. 6.
  16. M. Feingold and Y. Alhassid (to be published).

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