ELECTRON IMPLICATIONS OF VALENT MOLECULAR ORBITALS IN THE POPULATION OF AnO2 (An = Th – Lr) RELATIONSHIPS

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Abstract

Abstract. The dependence of contributions of electrons of valence molecular orbitals (MOs) of AnO2 (An = Th – Lr) to bond occupancies (according to Malliken) on the atomic number Z has been obtained by the relativistic method of discrete variation. It has been observed that electrons of external valence MOs (VVMOs) strengthen the bonding, while electrons of internal valence MOs (IVMOs) weaken such bonding on average by one-third. The efficiency (observed in the experiment) of VVMO formation characterizes the peculiarity of chemical bonding of actinide dioxides. With increasing Z, the influence of valence MO electrons on the covalent bond significantly decreases and it acquires a more ionic character. Significant effects of covalent bonding in AnO2 are observed due to the overlap of not only An 6d- but also An 6p- and An 5f-atomic orbitals with ligand orbitals.

About the authors

A. E Putkov

National Research Center "Kurchatov Institute"

Moscow, Russia

Yu. A Teterin

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

Moscow, Russia; Moscow, Russia

M. V Ryzhkov

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

Ekaterinburg, Russia

K. I Maslakov

Lomonosov Moscow State University

Moscow, Russia

A. Yu Teterin

National Research Center "Kurchatov Institute"

Email: antonxray@yandex.ru
Moscow, Russia

K. E Ivanov

National Research Center "Kurchatov Institute"

Moscow, Russia

S. N Kalmykov

Lomonosov Moscow State University

Moscow, Russia

V. G Petrov

Lomonosov Moscow State University

Moscow, Russia

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