Relativity and the chemistry of UF{sub 6}: A molecular Dirac-Hartree-Fock-CI study

Journal Article · Mon Apr 15 04:00:00 EDT 1996 · International Journal of Quantum Chemistry

DOI:https://doi.org/10.1002/(SICI)1097-461X(1996)58:2<203::AID-QUA9>3.0.CO;2-1· OSTI ID:447673

De Jong, W A; Nieuwpoort, W C ^[1]

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1. Univ. of Groningen (Netherlands)

The electronic structure and bonding of UF{sub 6} and UF{sub 6}{sup {minus}} are studied within a relativistic framework using the MOLFDIR program package. A stronger bonding but more ionic molecule is found if one compares the relativistic with the nonrelativistic results. The first peak in the photoelectron spectrum of Karlsson et al. is assigned to the 12{gamma}{sub 8u} component of the 4t{sub 1u} orbital, in agreement with other theoretical and experimental results. Good agreement is found between the experimental and theoretical 5{integral} spectrum UF{sub 6}{sup {minus}}. Some properties, like the dissociation energy and electron affinity, are calculated and the necessity of a fully relativistic framework is shown. The Breit interaction has an effect on the core spinors and the spin-orbit splitting of these spinors but the influence on the valence spectrum is negligible. 42 refs., 2 figs, 14 tabs.

• OSTI ID: 447673
• Journal Information: International Journal of Quantum Chemistry, Journal Name: International Journal of Quantum Chemistry Journal Issue: 2 Vol. 58; ISSN IJQCB2; ISSN 0020-7608
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
66 PHYSICS
CONFIGURATION INTERACTION
DISSOCIATION ENERGY
ELECTRONIC STRUCTURE
HARTREE-FOCK METHOD
MATHEMATICAL MODELS
PHOTOELECTRON SPECTROSCOPY
URANIUM FLUORIDES