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Title: Charge transfer vibronic transitions in uranyl tetrachloride compounds;

Abstract

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-resolvedmore » spectroscopic studies. The present empirical simulation provides insights into fundamental understanding of uranyl electronic interactions and is useful for quantitative characterization of uranyl coordination.« less

Authors:
; ;  [1]
  1. Chemical Sciences and Engineering Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1035766
Report Number(s):
ANL/CSE/JA-71523
Journal ID: ISSN 1089-5639; JPCAFH; TRN: US201205%%381
DOE Contract Number:  
DE-AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory
Additional Journal Information:
Journal Volume: 116; Journal Issue: 2; Journal ID: ISSN 1089-5639
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION; BOND LENGTHS; EXCITATION; EXCITED STATES; GROUND STATES; HELIUM; LUMINESCENCE; PHOTOLUMINESCENCE; RESOLUTION; SIMULATION; SPECTRA; SUPERLATTICES

Citation Formats

Liu, G K, Deifel, N P, Cahill, C L, and George Washington University). Charge transfer vibronic transitions in uranyl tetrachloride compounds;. United States: N. p., 2012. Web. doi:10.1021/jp210046j.
Liu, G K, Deifel, N P, Cahill, C L, & George Washington University). Charge transfer vibronic transitions in uranyl tetrachloride compounds;. United States. https://doi.org/10.1021/jp210046j
Liu, G K, Deifel, N P, Cahill, C L, and George Washington University). 2012. "Charge transfer vibronic transitions in uranyl tetrachloride compounds;". United States. https://doi.org/10.1021/jp210046j.
@article{osti_1035766,
title = {Charge transfer vibronic transitions in uranyl tetrachloride compounds;},
author = {Liu, G K and Deifel, N P and Cahill, C L and George Washington University)},
abstractNote = {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.},
doi = {10.1021/jp210046j},
url = {https://www.osti.gov/biblio/1035766}, journal = {Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory},
issn = {1089-5639},
number = 2,
volume = 116,
place = {United States},
year = {Sun Jan 01 00:00:00 EST 2012},
month = {Sun Jan 01 00:00:00 EST 2012}
}