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Ab initio studies of the electronic structrue of UF/sub 6/, UF/sub 6//sup +/, and UF/sup -//sub 6/ using relativistic effective core potentials

Journal Article · · J. Chem. Phys.; (United States)
OSTI ID:6096512
Ab initio calculations are performed on the electronic states of UF/sub 6/, UF/sub 6//sup +/, and UF/sup -//sub 6/ using a relativistic effective core potential (ECP) for uranium and a nonrelativistic ECP for fluorine. In most of the calculations 56 valence electrons are treated explicitly using a contracted (3s3p2d2f/2s2p) Gaussian basis. Various ECP's were explored, but all yield an overall charge density of U/sup +2.4/ (F/sup -0.4/)/sub 6/. The bonding in the ground state of UF/sub 6/ is discussed. SCF and CI calculations on UF/sub 6//sup +/ are compared with the experimental photoelectron spectrum and with previous scattered-wave calculations. The role of spin--orbit coupling in the states of UF/sub 6//sup +/ and UF/sub 6//sup -/ is discussed. The calculated electron affinity of UF/sub 6/ (7.1 eV) is considerably larger than the current experimental estimates, but the relative energies of the states of UF/sub 6//sup -/ are in excellent agreement (0.1--0.2 eV) with experiment.
Research Organization:
Theoretical Division, University of California, Los Alamos Scientific Laboratory, Los Alamos, New Mexico 87545
OSTI ID:
6096512
Journal Information:
J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 71:4; ISSN JCPSA
Country of Publication:
United States
Language:
English