Temperature Dependence of Nuclear Quadrupole Resonance and the Observation of Metal–Ligand Covalency in Actinide Complexes: 35Cl in Cs2UO2Cl4

Park, Sejun; Walter, Eric D.; Soderquist, Chuck Z.; Sinkov, Sergey I.; Cho, Herman

doi:10.1021/acs.jpca.3c04657

Title: Temperature Dependence of Nuclear Quadrupole Resonance and the Observation of Metal–Ligand Covalency in Actinide Complexes: ³⁵Cl in Cs₂UO₂Cl₄

Journal Article · 28 September 2023 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI: https://doi.org/10.1021/acs.jpca.3c04657 · OSTI ID:2328121

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Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)

We report a study of the temperature dependence of ³⁵Cl nuclear quadrupole resonance (NQR) transition energies and spin–lattice relaxation times (T₁) for ²³⁵U-depleted dicesium uranyl tetrachloride (Cs₂UO₂Cl₄) aimed at elucidating electronic interactions between the uranium center and atoms in the equatorial plane of the UO₂²⁺ ion. The transition frequency decreases slowly with temperature below 75 K and with a more rapid linear dependence above this temperature. The spin–lattice relaxation time becomes shorter with temperature, and as temperatures increase, the T₁ decrease becomes nearly quadratic. The observed trends are reproduced by a model that assumes phonon-induced fluctuations of the electric field gradient tensor and partial electron delocalization from Cl to U. The fit of the theoretical model to experimental data allows a Debye temperature of 96 K to be estimated. Finally, the generalization of this approach to investigations of covalency in actinide–ligand bonding is examined.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 2328121

Report Number(s):: PNNL-SA--185388

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 40 Vol. 127; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Title: Temperature Dependence of Nuclear Quadrupole Resonance and the Observation of Metal–Ligand Covalency in Actinide Complexes: 35Cl in Cs2UO2Cl4

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Title: Temperature Dependence of Nuclear Quadrupole Resonance and the Observation of Metal–Ligand Covalency in Actinide Complexes: ³⁵Cl in Cs₂UO₂Cl₄