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Structure of the XPS Spectra of a ThO2 Crystal Film

Abstract

The complex structure of precision X-ray photoelectron spectra (XPS) of valence and core electrons of a ThO2(001) crystal film on Si(100) was obtained and analyzed, and the electronic structure of ThO8, Th13O56, and Th63O216 clusters was calculated. A histogram of the calculated XPS spectrum of electrons of the outer (from 0 to ~15 eV, OVMO) and inner (from ~15 to ~35 eV, IVMO) valence MOs was plotted. The calculated spectrum was in good agreement with the experimental one. Significant overlap of Th 6d atomic orbitals (AO) as well as Th 6p, 5f AO with oxygen orbitals is noted, which brings about the covalent nature of the bond in this dioxide. The contribution of the OVMO and IVMO electrons to the chemical bond was estimated based on the values of the bond populations. It was shown that the IVMO electrons weaken the chemical bond caused by OVMO electrons. It is assumed that the complex structure in the spectra of the Th 5s and Th 5p electrons is largely due to the dynamic effect, which does not allow observing the structure in the spectrum of the Th 5s electrons in ThO2.

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ACKNOWLEDGMENTS

Thanks to Thomas Gouder, Rachel Eloirdi, Alice Seibert of the European Commission, Joint Research Centre, Directorate of Nuclear Safety for producing the ThO2 thin film sample. Ian Farnan, Giulio Lampronti, and Aleksej Popel of the Faculty of Geosciences, University of Cambridge, for providing and characterizing the sample with SEM, XRF, and EBSD.

Funding

This work was supported by RFBR grant no. 20-03-00333 and was performed using equipment purchased at the expense of the Development Program of Moscow State University.

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Correspondence to Yu. A. Teterin.

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Putkov, A.E., Maslakov, K.I., Teterin, A.Y. et al. Structure of the XPS Spectra of a ThO2 Crystal Film. Radiochemistry 64, 133–142 (2022). https://doi.org/10.1134/S1066362222020035

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  • DOI: https://doi.org/10.1134/S1066362222020035

Keywords:

  • thorium dioxide
  • X-ray photoelectron spectra
  • quantum chemical calculations