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Title: Magnetic circular dichroism of UCl 6– in the ligand-to-metal charge-transfer spectral region

Here, we present a combined ab initio theoretical and experimental study of the magnetic circular dichroism (MCD) spectrum of the octahedral UCl 6- complex ion in the UV-Vis spectral region. The ground state is an orbitally non-degenerate doublet E 5/2u and the MCD is a $C$-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 $C$-terms: Under O h double group symmetry, E 5/2u → E 5/2g transitions have negative $C$-terms whereas E 5/2u → F 3/2g transitions have positive $C$-terms if the ground state g-factor is negative, as it is the case for UCl 6-.
Authors:
 [1] ;  [2] ;  [1] ;  [3] ;  [3] ;  [3] ; ORCiD logo [3] ;  [4] ;  [5] ;  [1]
  1. Univ. at Buffalo, NY (United States). Dept. of Chemistry
  2. Univ. of Rochester, NY (United States). Dept. of Chemistry
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  4. Univ. of Toulouse (France). Lab. de Physique et de Chimie Quantiques
  5. Univ. of Rochester, NY (United States). Dept. of Chemistry
Publication Date:
Report Number(s):
LA-UR-17-23360
Journal ID: ISSN 1463-9076
Grant/Contract Number:
AC52-06NA25396; FG02-09ER16066; SC0001136; SC0016002
Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 19; Journal Issue: 26; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Research Org:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org:
USDOE Office of Science (SC). Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1371674

Gendron, Frederic, Fleischauer, Valerie R., Duignan, Thomas J., Scott, Brian L., Löble, Matthias W., Cary, Samantha K., Kozimor, Stosh Anthony, Bolvin, Helene, Neidig, Michael L., and Autschbach, Jochen. Magnetic circular dichroism of UCl6– in the ligand-to-metal charge-transfer spectral region. United States: N. p., Web. doi:10.1039/C7CP02572F.
Gendron, Frederic, Fleischauer, Valerie R., Duignan, Thomas J., Scott, Brian L., Löble, Matthias W., Cary, Samantha K., Kozimor, Stosh Anthony, Bolvin, Helene, Neidig, Michael L., & Autschbach, Jochen. Magnetic circular dichroism of UCl6– in the ligand-to-metal charge-transfer spectral region. United States. doi:10.1039/C7CP02572F.
Gendron, Frederic, Fleischauer, Valerie R., Duignan, Thomas J., Scott, Brian L., Löble, Matthias W., Cary, Samantha K., Kozimor, Stosh Anthony, Bolvin, Helene, Neidig, Michael L., and Autschbach, Jochen. 2017. "Magnetic circular dichroism of UCl6– in the ligand-to-metal charge-transfer spectral region". United States. doi:10.1039/C7CP02572F. https://www.osti.gov/servlets/purl/1371674.
@article{osti_1371674,
title = {Magnetic circular dichroism of UCl6– in the ligand-to-metal charge-transfer spectral region},
author = {Gendron, Frederic and Fleischauer, Valerie R. and Duignan, Thomas J. and Scott, Brian L. and Löble, Matthias W. and Cary, Samantha K. and Kozimor, Stosh Anthony and Bolvin, Helene and Neidig, Michael L. and Autschbach, Jochen},
abstractNote = {Here, 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 $C$-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 $C$-terms: Under Oh double group symmetry, E5/2u → E5/2g transitions have negative $C$-terms whereas E5/2u → F3/2g transitions have positive $C$-terms if the ground state g-factor is negative, as it is the case for UCl6-.},
doi = {10.1039/C7CP02572F},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 26,
volume = 19,
place = {United States},
year = {2017},
month = {6}
}

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