Photophysical studies of uranyl complexes 5. Luminescence spectrum of K4UO2(CO3)3 |
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Authors: | Harry G Brittain Leon Tsao Dale L Perry |
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Institution: | Department of Chemistry, Seton Hall University, South Orange, NJ 07079, USA;Lawrence Berkeley Laboratory, University of California, Berkeley, CA 94720, USA |
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Abstract: | The photoluminescence of K4UO2(CO3)3 has been studied under conditions of high resolution at cryogenic temperatures. The origin corresponding to the pure electronic transition was located at 4774 Å (20945 cm-1), and it was found that the totally symmetric uranyl stretching mode was coupled to this transition. A progression of four band systems thus resulted, and from an examination of the energies of corresponding peaks in each system, a value of 813 cm-1 for the U-O stretching mode was determined. Two lattice modes (34 and 80 cm-1) and two molecular vibrational modes (205 and 276 cm-1) were also found to couple with the pure electronic transition, thus yielding approximately 15 major peaks in each band system. The 205 cm-1 vibration corresponded to a CO2-3 vibration, while the 276 cm-1 vibration was a UO2+2 deformation. The low values obtained for the force constant and totally symmetric stretching frequency of the U-O bond suggested that in UO2(CO)4-3, the uranium atom is bound in a complex species that may be considered as an intermediate between that of a uranyl (UO2+2) and a uranate (UO10-8) ion. |
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