Characterization of the Fine Valence XPS Structure of Actinide Dioxides on the Basis of the Electronic Structure Modeling

For the first time, theoretical dependences of the width Г(eV) of the X-ray photoelectron spectra of the outer (OVMO) and inner (IVMO) valence molecular orbitals electrons without taking into account the An 6s electrons, as well as the intensities ratio of these spectra (I/I = OVMO/IVMO) calculated by the relativistic discrete variation method for AnO (An = Th–Lr) have been obtained depending on the atomic number Z. Satisfactory agreement has been established with the available relevant experimental data for AnO of light actinides. The decrease in the OVMO XPS width in the Pa–Lr series is associated with a shift in the partial density of states of the An 5 electrons to the OVMO bottom while the increase in the IVMO width is mainly due to an increase in the magnitude of the spin-orbit splitting (ΔE) of the An 6-electrons. It has been found that the OVMO intensity is mainly related to the An 5- and 6-electrons, since the photoionization cross sections for these electrons are significantly larger than those for the An 7-, 7-, and O 2-electrons.

Keywords

диоксиды актиноидов внешние и внутренние валентные МО теоретические и экспериментальные спектры РФЭС

Date of publication

24.03.2026

Year of publication

2026

Number of purchasers

Views

References

1. Katz J.J., Seaborg G.T., MorssKatz J.J., Seaborg G.T., Morss L.R. The chemistry of the actinide elements. L.; N.Y.: Chapman and Hall, 1986.
2. Teterin Yu.A., Teterin A.Yu. Structure of X-ray photoelectron spectra of light actinide compounds // Russ. Chem. Rev. 2004. V. 73. P. 541. https://doi.org/10.1070/RC2004v07n06ABEH000821
3. Legg F., Harding L.M., Lewis J.C., Nicholls R., Green H., Steele H., Springell R. Epitaxial light actinide oxide thin films // Thin Solid Films. 2024. V. 790. P. 140194. http://dx.doi.org/10.2139/ssrn.4573818
4. Rai B.K., Bretana A., Morrison G., Greer R., Gofryk K., zur Loye H.-C. Crystal structure and magnetism of actinide oxides: a review // Rep. Prog. Phys. 2024. V. 87. № 6. P. 066501. https://doi.org/10.48550/arXiv.2403.01634
5. Pereiro F.A., Galley S.S., Jackson J.A., Shafer J.C. Contemporary assessment of energy degeneracy in orbital mixing with tetravalent f-block compounds // Inorg. Chem. 2024. V. 63. P. 9687. https://doi.org/10.1021/acs.inorgchem.3c03828
6. Ryzhkov M.V., Kupryazhkin A.Ya. First-principles study of electronic structure and insulating properties of uranium and plutonium dioxides // J. Nucl. Mater. 2009. V. 384. P. 226. https://doi.org/10.1016/j.jnucmat.2008.11.011
7. Teterin Yu.A., Tetetrin A.Yu. Modern X-ray spectral methods in the study of the electronic structure of actinide compounds: uranium oxide uO2 as an example // Nucl. Techn. Rad. Prot. 2004. V. 2. P. 3. https://doi.org/10.2298/NTRP0402003T
8. Wang D., van Gunstren W., Chain Z. Recent advances in computational actinoid chemistry // Chem. Soc. Rev. 2012. V. 41. P. 5836. https://doi.org/10.1039/c2cs15354h
9. Wang J., Ewing R.C., Becker U. Electronic structure and stability of hyperstoichiometric uO2+x under pressure // Phys. Rev. B. 2013. V. 88. P. 024109. https://doi.org/10.1103/PhysRevB.88.024109
10. Wen X.-D., Martin R.L., Henderson T.M., Scuseria G.E. Density functional theory studies of the electronic structure of solid state actinide oxides // Chem. Rev. 2013. V. 113. P. 1063. https://doi.org/10.1021/cr300374y
11. Zaitsevskii A., Skripnikov L.V., Titov A.V. Chemical bonding and effective atomic states of actinides in higher oxide molecules // Mendeleev Commun. 2016. V. 26. P. 307. https://doi.org/10.1016/j.mencom.2016.07.013
12. Gouder T., Seibert A., Havela L., Rebizant J. Search for higher oxides of Pu: A photoemission study // Surf. Sci. 2007. V. 601. P. L77. https://doi.org/10.1016/j.susc.2007.04.259
13. Seibert A., Gouder T., Huber F. Formation and stability of actinide oxides: a valence band photoemission study // Radiochim. Acta. 2009. V. 97. № 4–5. P. 247. https://doi.org/10.1524/ract.2009.1605
14. Idriss H. Surface reactions of uranium oxide powder, thin films and single crystals // Surf. Sci. Rep. 2010. V. 65. P. 67. https://doi.org/10.1016/j.surfrep.2010.01.001
15. Veal B.W., Diamond H., Hoekstra H.R. X-ray photoelectron-spectroscopy study of oxides of the transuranium elements Np, Pu, Am, Cm, Bk and Cf // Phys. Rev. B. 1977. V. 15. P. 2929. https://doi.org/https://doi.org/10.1103/PhysRevB.15.2929
16. Rosen A., Ellis D.E. Relativistic molecular calculations in the Dirac–Slater model // J. Chem. Phys. 1975. V. 62. P. 3039. https://doi.org/10.1063/1.430892
17. Adachi H. Relativistic molecular orbital theory in the Dirac–Slater model // Technol. Rep. Osaka univ. 1972. V. 1392. P. 569.
18. Gunnarsson O., Lundqvist B.I. Exchange and correlation in atoms, molecules and solids by the spin-density-functional formalism // Phys. Rev. B. 1976. V. 13. P. 4274. https://doi.org/10.1103/PhysRevB.13.4274
19. Pyykko P., Toivonen H. Tables of representation and rotation matrices for the relativistic irreducible representations of 38 point groups // Acta Acad. Aboensis. Ser. B. 1983. V. 43. 50 p.
20. Varshalovish D.A., Moskalev A.N., Khersonskii V.K. Quantum Theory of Angular Momentum. Singapore: World Scientific, 1988. 439 p.
21. Teterin Yu.A., Ryzhkov M.V., Putkov A.E., Maslakov K.I., Teterin A.Yu., Ivanov K.E., Kalmykov S.N., Petrov V.G. Chemical bond nature and structure of X-ray photoelectron spectrum of PaO2 // Russ. J. Inorg. Chem. 2022. V. 67. № 6. P. 881. https://doi.org/10.1134/S0036023622060274
22. Тетерин Ю.А., Маслаков К.И., Рыжков М.В., Трапарич О.А., Вукчевич Л., Тетерин А.Ю., Панов А.Д. Природа химической связи в диоксиде урана uO2 // Радиохимия. 2005. Т. 47. № 3. С. 193.
23. Maslakov K.I., Teterin Yu.A., Ryzhkov M.V., Popel A.J., Teterin A.Yu., Ivanov K.E., Kalmykov S.N., Petrov V.G., Farnan I. The nature of the chemical bond in uO2 // Int. J. Quantum Chem. 2019. P. 119:e26040. https://doi.org/10.1002/qua.26040.
24. Ryzhkov M.V., Kovalenko M.A., Kupryazhkin A.Ya., Gupta S.K. Electronic structure and effective charges on atoms near anion point defects in uranium dioxide // Comp. Condens Matter. 2019. V. 18. P. e00353-9. https://doi.org/10.1016/j.cocom.2018.e00353
25. Ryzhkov M.V., Kovalenko M.A., Kupryazhkin A.Ya., Gupta S.K. Transformation of electron density distribution induced by the cation point defects in uranium dioxide // J. Radioanal. Nucl. Chem. 2020. V. 325. P. 253. https://doi.org/10.1007/s10967-020-07228-z
26. Teterin Yu.A., Teterin A.Yu., Ivanov K.E., Ryzhkov M.V., Maslakov K.I., Kalmykov St.N., Petrov V.G., Enina D.A. X-ray photoelectron spectra structure and chemical bond nature in NpO2 // Phys. Rev. B. 2014. V. 89. P. 035102. https://doi.org/10.1103/PhysRevB.89.035102
27. Teterin Yu.A., Maslakov K.I., Teterin A.Yu., Ivanov K.E., Ryzhkov M.V., Petrov V.G., Enina D.A., Kalmykov St.N. Electronic structure and chemical bonding in PuO2 // Phys. Rev. B. 2013. V. 87. P. 245108. https://doi.org/10.1103/PhysRevB.87.245108
28. Gelius U., Allan C.J., Johansson G., Siegbahn H., Allison D.A., Siegbahn K. The ESCA spectra of benzene and Thei-electronic series, thiophene, pyrrole and furan // Phys. Scr. 1971. V. 3. P. 237. https://doi.org/10.1088/0031-8949/3/5/008
29. Yarzhemsky V.G., Nefedov V.I., Amusya M.Ya., Cherepkov N.A., Chernysheva L.V. Relative intensities in X-ray photoelectron spectra part VIII // J. Electron. Spectr. Relat. Phenom. 1981. V. 23. № 2. P. 175. https://doi.org/10.1016/0368-2048 (81)80033-3
30. Yarzhemsky V.G., Teterin A.Yu., Teterin Yu.A., Trzhaskovskaya M.B. Photoionization cross sections of ground and excited valence levels of actinides // Nucl. Techn. Rad. Prot. 2012. V. 27. P. 103. https://doi.org/10.2298/NTRP1202103Y
31. Putkov A.E., Teterin Yu.A., Ryzhkov M.V., Teterin A.Yu., Maslakov K.I., Ivanov K.E., Kalmykov S.N., Petrov V.G. Electronic structure and nature of chemical bonds in BkO2 // Russ. J. Phys. Chem. A. 2021. V. 95. № 6. P. 1169. https://doi.org/10.1134/S0036024421060212

GOST	Ivanov K., Kalmykov S., Maslakov K., Petrov V., Putkov A., Ryzhkov M., Teterin Y., Teterin A. Characterization of the Fine Valence XPS Structure of Actinide Dioxides on the Basis of the Electronic Structure Modeling // Inorganic Materials. – 2025. – V. 61. – Issue number 9-10 C. 570-581 . URL: https://inorgmaterialsras.ru/s3034558825050055-1/?version_id=125532. DOI: 10.7868/S3034558825050055
MLA	Ivanov, K.E, Kalmykov, S.N, Maslakov, K.I, Petrov, V.G, Putkov, A.E, Ryzhkov, M.V, Teterin, Yu.A, Teterin, A.Yu "Characterization of the Fine Valence XPS Structure of Actinide Dioxides on the Basis of the Electronic Structure Modeling." Inorganic Materials. 61.9-10 (2025).:570-581. DOI: 10.7868/S3034558825050055
APA	Ivanov K., Kalmykov S., Maslakov K., Petrov V., Putkov A., Ryzhkov M., Teterin Y., Teterin A. (2025). Characterization of the Fine Valence XPS Structure of Actinide Dioxides on the Basis of the Electronic Structure Modeling. Inorganic Materials. vol. 61, no. 9-10, pp.570-581 DOI: 10.7868/S3034558825050055

RAS Chemistry & Material ScienceНеорганические материалы Inorganic Materials

Characterization of the Fine Valence XPS Structure of Actinide Dioxides on the Basis of the Electronic Structure Modeling

You can

References

Indexing

RAS Chemistry & Material ScienceНеорганические материалы Inorganic Materials

Characterization of the Fine Valence XPS Structure of Actinide Dioxides on the Basis of the Electronic Structure Modeling

You can

References

Indexing

Via social network