Charge transfer vibronic transitions in uranyl tetrachloride compounds;

Journal Article · Sun Jan 01 04:00:00 EST 2012 · Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory

DOI:https://doi.org/10.1021/jp210046j· OSTI ID:1035766

Liu, G K; Deifel, N P; Cahill, C L ^[1]

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1. Chemical Sciences and Engineering Division

The electronic and vibronic interactions of uranyl (UO{sub 2}){sup 2+} in three tetrachloride crystals have been investigated with spectroscopic experiments and theoretical modeling. Analysis and simulation of the absorption and photoluminescence spectra have resulted in a quantitative understanding of the charge transfer vibronic transitions of uranyl in the crystals. The spectra obtained at liquid helium temperature consist of extremely narrow zero-phonon lines (ZPL) and vibronic bands. The observed ZPLs are assigned to the first group of the excited states formed by electronic excitation from the 3{sigma} ground state into the f{sub {delta}{phi}}, orbitals of uranyl. The Huang-Rhys theory of vibronic coupling is modified successfully for simulating both the absorption and luminescence spectra. It is shown that only vibronic coupling to the axially symmetric stretching mode is Franck-Condon allowed, whereas other modes are involved through coupling with the symmetric stretching mode. The energies of electronic transitions, vibration frequencies of various local modes, and changes in the O=U=O bond length of uranyl in different electronic states and in different coordination geometries are evaluated in empirical simulations of the optical spectra. Multiple uranyl sites derived from the resolution of a superlattice at low temperature are resolved by crystallographic characterization and time- and energy-resolved spectroscopic studies. The present empirical simulation provides insights into fundamental understanding of uranyl electronic interactions and is useful for quantitative characterization of uranyl coordination.

• Research Organization: Argonne National Laboratory (ANL)
• Sponsoring Organization: SC
• DOE Contract Number: AC02-06CH11357
• OSTI ID: 1035766
• Report Number(s): ANL/CSE/JA-71523
• Journal Information: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory, Journal Name: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory Journal Issue: 2 Vol. 116; ISSN 1089-5639; ISSN JPCAFH
• Country of Publication: United States
• Language: ENGLISH

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ABSORPTION
BOND LENGTHS
EXCITATION
EXCITED STATES
GROUND STATES
HELIUM
LUMINESCENCE
PHOTOLUMINESCENCE
RESOLUTION
SIMULATION
SPECTRA
SUPERLATTICES