Jump to main content
Jump to site search

Issue 26, 2017
Previous Article Next Article

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

Author affiliations

Abstract

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

Back to tab navigation

Supplementary files

Publication details

The article was received on 19 Apr 2017, accepted on 31 May 2017 and first published on 23 Jun 2017


Article type: Paper
DOI: 10.1039/C7CP02572F
Citation: Phys. Chem. Chem. Phys., 2017,19, 17300-17313
  •   Request permissions

    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

Search articles by author

Spotlight

Advertisements