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Direct measurement of 5f delocalization with U XES

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Abstract

Delocalization of the 5f states in the early actinides in general and U metal in particular is significantly important and yet poorly understood. Extant spectroscopic techniques have failed to resolve the situation. Here, it will be shown that x-ray emission spectroscopy of the M4,5 levels can provide the needed information, with a distinct difference between the delocalized U metal and localized uranium dioxide and uranium tetrafluoride cases. A peak ratio model, built upon electric dipole selection rules, has been developed and utilized, with quantitative agreement between experiment and theory. Possible expansion to other types of 5f mixing systems will be discussed.

Impact statement

Delocalization of the 5f states in the actinides is problematic. While the atomic size variation in the light actinides indicates that delocalization is vitally important, the conventional tool for the characterization of delocalization, angle-resolved photoelectron spectroscopy and bandmapping, fails. Here, we report the first utilization of UM x-ray emission spectroscopy (XES) as a probe of 5f delocalization. Historically, x-ray absorption spectroscopy into the 5f states has played a key role in the characterization of the 5f occupation. In this article, it is laid out how XES from the 5f states can play a similarly important role in quantifying 5f delocalization. This article includes novel experimental measurements and a quantitative theoretical modeling. The technological innovation that permits these measurements is the new and powerful facility at the Stanford Synchrotron Radiation Lightsource at the SLAC National Accelerator Laboratory for tender x-ray measurements, in the regime between hard and soft x-rays.

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Acknowledgments

Stanford Synchrotron Radiation Lightsource is a national user facility operated by Stanford University on behalf of the DOE and the OBES. Part funding for the instrument used for this study came from the US Department of Energy, Office of Energy Efficiency & Renewable Energy, Solar Energy Technology Office BRIDGE Program. Resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the US Department of Energy under Contract No. DE-AC02-05CH11231, were used in this work. LLNL is operated by Lawrence Livermore National Security, LLC, for the US Department of Energy, National Nuclear Security Administration, under Contract DE-AC52-07NA27344.

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Authors and Affiliations

  1. University of Wisconsin–Oshkosh, Oshkosh, USA

    J. G. Tobin

  2. SLAC National Accelerator Laboratory, Menlo Park, USA

    S. Nowak, R. Alonso-Mori, T. Kroll, D. Nordlund, T.- C. Weng & Dimosthenis Sokaras

  3. Lawrence Livermore National Laboratory, Livermore, USA

    S.- W. Yu

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  1. J. G. Tobin
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  2. S. Nowak
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Correspondence to J. G. Tobin or Dimosthenis Sokaras.

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Tobin, J.G., Nowak, S., Yu, S.W. et al. Direct measurement of 5f delocalization with U XES. MRS Bulletin 47, 1078–1083 (2022). https://doi.org/10.1557/s43577-022-00419-x

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