ELECTRONIC STRUCTURE AND CHEMICAL BONDING IN EsO2

• Published in: Journal of structural chemistry Vol. 64; no. 9; pp. 1644 - 1653
• Main Authors: Teterin, Y. A., Ryzhkov, M. V., Putkov, A. E., Maslakov, K. I., Teterin, A. Y., Ivanov, K. E., Kalmykov, S. N., Petrov, V. G.
• Format: Journal Article
• Language: English
• Published: Moscow Pleiades Publishing 01-09-2023; Springer Nature B.V
• Subjects: Atomic; Atomic/Molecular Structure and Spectra; Bonding strength; Chemical bonds; Chemistry; Chemistry and Materials Science; Dioxides; Electronic structure; Electrons; Inorganic Chemistry; Molecular; Molecular orbitals; Optical and Plasma Physics; Photoelectric effect; Photoelectricity; Photoelectrons; Physical Chemistry; Solid State Physics; X ray photoelectron spectroscopy; EsO; outer valence (OVMO) and inner valence (IVMO) molecular orbitals; DVM method; structure of XPS valence band spectra; actinide dioxides; electronic structure
• ISSN: 0022-4766; 1573-8779
• DOI: 10.1134/S0022476623090081

The density of states of valence electrons of the EsO
2
dioxide is calculated by the relativistic discrete variational method. The scheme of valence molecular orbitals (MOs) is constructed taking into account the photoelectric effect cross sections of valence electrons. The histogram of X-ray photoelectron spectra (XPS) is built for the electron binding energies from 0 eV to ~40 eV. It is shown that the structure of this spectrum contains contributions of outer valence orbitals (OVMOs, from 0 eV to ~15 eV) and inner valence orbitals (IVMOs, from ~15 eV to ~50 eV) molecular orbitals. It is established that Es 5
f
and Es 6
p
electrons participate in the chemical bonding. It is established that not only Es 6
d
, but also Es 6
p
and Es 5
f
orbitals overlap significantly with ligand orbitals, resulting in a highly covalent chemical bonding in this dioxide. The nature of chemical bonding and the structure of the XPS spectrum of valence electrons in EsO
2
is clarified using the scheme of MOs. It is shown that the chemical bonding formed by OVMO electrons is weaken by one third due to IVMO electrons.