We present a scaling technique to analyze quantum spectra, i.e., to obtain from quantum calculations detailed information about the underlying important classical motions. The method can be applied to a general quantum system without a classical scaling property. A demonstration on the conventionally unassignable vibrational spectrum of the radical reveals remnants of classical broken tori embedded in the chaotic phase space and leads to a new assignment of spectral patterns in terms of classical Fermi resonances between the local mode motions. The scaling technique also allows to investigate the statistical properties of level spacings at fixed energies. The nearest neighbor spacing distribution of the molecule undergoes a transition from mixed phase space behavior at low energies to the Wigner distribution characteristic for chaotic systems at energies near the dissociation threshold.
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1 November 1997
Research Article|
November 01 1997
Extracting the dynamics in classically chaotic quantum systems: Spectral analysis of the molecule
Jörg Main;
Jörg Main
Institut für Theoretische Physik I, Ruhr-Universität Bochum, D-44780 Bochum, Germany
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Christof Jung;
Christof Jung
UNAM Instituto de Matematicas, Unidad Cuernavaca, Av. Universidad s/n, 62251, Cuernavaca, Mexico
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Howard S. Taylor
Howard S. Taylor
Department of Chemistry, University of Southern California, Los Angeles, California 90089
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J. Chem. Phys. 107, 6577–6583 (1997)
Article history
Received:
May 19 1997
Accepted:
July 30 1997
Citation
Jörg Main, Christof Jung, Howard S. Taylor; Extracting the dynamics in classically chaotic quantum systems: Spectral analysis of the molecule. J. Chem. Phys. 1 November 1997; 107 (17): 6577–6583. https://doi.org/10.1063/1.474900
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