Relativistic electronic structure of UO/sub 2//sup + +/, UO/sub 2//sup +/, and UO/sub 2/

Journal Article · Fri May 01 04:00:00 EDT 1981 · J. Chem. Phys.; (United States)

OSTI ID:6439559

Wood, J H; Boring, M; Woodruff, S B

We have calculated the one-electron energy level structures of the isolated species UO/sub 2//sup + +/, UO/sub 2//sup +/, and UO/sub 2/ in their linear forms, using a self-consistent relativistic multiple scattering model with Xa exchange. For UO/sub 2//sup + +/, we have used the molecular orbitals of the ground state muffin-tin potential to calculate the energies of a few of the many-electron excited states; these afford a somewhat more fundamental basis for comparison with experiment than do the one-electron energies, and their determination also sheds some light on the coupling scheme (w--w vs L--S) to be expected in these systems. These excited state energies agree well with the experimental absorption data. The calculated one-electron excitation energies for UO/sub 2//sup + +/ are in reasonable agreement with the observed onset of absorption. The behavior of the corresponding one-electron binding energies as a function of U--O distance supports a different interpretation of the XPS than that given by Veal et al. Considering the three species at a common bond distance of 2.0 A, we find that each contains roughly three 5f electrons; UO/sub 2//sup + +/ has three bonding 5f 's, UO/sub 2//sup +/ has two bonding 5f 's and one nonbonding (localized) 5f, and UO/sub 2/ has one bonding 5f and two nonbonding 5f 's. This agrees with XPS which exhibits two localized f electrons in UO/sub 2/ and none in UO/sub 2//sup + +/.

• Research Organization: Los Alamos National Laboratory, University of California, Los Alamos, New Mexico 87545
• OSTI ID: 6439559
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 74:9; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
ACTINIDE COMPOUNDS
BINDING ENERGY
CHALCOGENIDES
CHARGED PARTICLES
ELECTRONIC STRUCTURE
ENERGY
ENERGY LEVELS
FIELD THEORIES
GENERAL RELATIVITY THEORY
IONS
MOLECULAR IONS
OXIDES
OXYGEN COMPOUNDS
RELATIVITY THEORY
SELF-CONSISTENT FIELD
URANIUM COMPOUNDS
URANIUM DIOXIDE
URANIUM OXIDES