Phase space structure of triatomic molecules

Journal Article · Tue Jul 01 04:00:00 EDT 1997 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.474366· OSTI ID:530056

Lu, Z; Kellman, M E ^[1]

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1. Department of Chemistry, University of Oregon, Eugene, Oregon 97403 (United States)

The bifurcation structure is investigated for a Hamiltonian for the three coupled nonlinear vibrations of a highly excited triatomic molecule. The starting point is a quantum Hamiltonian used to fit experimental spectra. This Hamiltonian includes 1:1 Darling{endash}Dennison resonance coupling between the stretches, and 2:1 Fermi resonance coupling between the stretches and bend. A classical Hamiltonian is obtained using the Heisenberg correspondence principle. Surfaces of section show a pronounced degree of chaos at high energies, with a mixture of chaotic and regular dynamics. The large-scale bifurcation structure is found semianalytically, without recourse to numerical solution of Hamilton{close_quote}s equations, by taking advantage of the fact that the spectroscopic Hamiltonian has a conserved polyad quantum number, corresponding to an approximate constant of the motion of the molecule. Bifurcation diagrams are analyzed for a number of molecules including H{sub 2}O, D{sub 2}O, NO{sub 2}, ClO{sub 2}, O{sub 3}, and H{sub 2}S. {copyright} {ital 1997 American Institute of Physics.}

• DOE Contract Number: FG06-92ER14236
• OSTI ID: 530056
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 1 Vol. 107; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

66 PHYSICS
BIFURCATION
CHLORINE OXIDES
EXCITED STATES
FERMI RESONANCE
HEAVY WATER
HYDROGEN SULFIDES
MOLECULES
NITROGEN DIOXIDE
OZONE
PHASE SPACE
VIBRATIONAL STATES
WATER