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Issue 26, 2017
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Magnetic circular dichroism of UCl6 in the ligand-to-metal charge-transfer spectral region

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We present a combined ab initio theoretical and experimental study of the magnetic circular dichroism (MCD) spectrum of the octahedral UCl6 complex ion in the UV-Vis spectral region. The ground state is an orbitally non-degenerate doublet E5/2u and the MCD is a Image ID:c7cp02572f-t1.gif-term spectrum caused by spin–orbit coupling. Calculations of the electronic spectrum at various levels of theory indicate that differential dynamic electron correlation has a strong influence on the energies of the dipole-allowed transitions and the envelope of the MCD spectrum. The experimentally observed bands are assigned to dipole-allowed ligand-to-metal charge transfer into the 5f shell, and 5f to 6d transitions. Charge transfer excitations into the U 6d shell appear at much higher energies. The MCD-allowed transitions can be assigned via their signs of the Image ID:c7cp02572f-t2.gif-terms: Under Oh double group symmetry, E5/2u → E5/2g transitions have negative Image ID:c7cp02572f-t3.gif-terms whereas E5/2u → F3/2g transitions have positive Image ID:c7cp02572f-t4.gif-terms if the ground state g-factor is negative, as it is the case for UCl6.

Graphical abstract: Magnetic circular dichroism of UCl6− in the ligand-to-metal charge-transfer spectral region

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Supplementary files

Article information

19 Apr 2017
31 May 2017
First published
23 Jun 2017

Phys. Chem. Chem. Phys., 2017,19, 17300-17313
Article type

Magnetic circular dichroism of UCl6 in the ligand-to-metal charge-transfer spectral region

F. Gendron, V. E. Fleischauer, T. J. Duignan, B. L. Scott, M. W. Löble, S. K. Cary, S. A. Kozimor, H. Bolvin, M. L. Neidig and J. Autschbach, Phys. Chem. Chem. Phys., 2017, 19, 17300
DOI: 10.1039/C7CP02572F

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