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

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Abstract

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 (IOVMO/IIVMO = OVMO/IVMO) calculated by the relativistic discrete variation method for AnO2 (An = Th–Lr) have been obtained depending on the atomic number Z. Satisfactory agreement has been established with the available relevant experimental data for AnO2 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 5f 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 (ΔEsl) of the An 6p-electrons. It has been found that the OVMO intensity is mainly related to the An 5f- and 6d-electrons, since the photoionization cross sections for these electrons are significantly larger than those for the An 7s-, 7p-, and O 2p-electrons.

About the authors

Yu. A Teterin

Lomonosov Moscow State University; National Research Center "Kurchatov Institute"

Moscow, Russian Federation; Moscow, Russian Federation

A. E Putkov

National Research Center "Kurchatov Institute"

Moscow, Russian Federation

M. V Ryzhkov

Institute of Solid State Chemistry, Ural Branch of the Russian Academy of Sciences

Yekaterinburg, Russian Federation

K. I Maslakov

Lomonosov Moscow State University

Moscow, Russian Federation

A. Yu Teterin

National Research Center "Kurchatov Institute"

Email: antonxray@yandex.ru
Moscow, Russian Federation

K. E Ivanov

National Research Center "Kurchatov Institute"

Moscow, Russian Federation

S. N Kalmykov

National Research Center "Kurchatov Institute"

Moscow, Russian Federation

V. G Petrov

Lomonosov Moscow State University

Moscow, Russian Federation

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