Electronic structure and spectra of uranocene

The wave functions and energy levels for uranocene, U(C{sub 8}H{sub 8}){sub 2}, have been computed using ab initio techniques including the spin-orbit interaction and relativistic core potentials. The results give detailed information on the bonding in the ground state and on the assignment of the v...

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Bibliographic Details
Published inJournal of the American Chemical Society Vol. 111:7
Main Authors Chang, A.H.H., Pitzer, R.M.
Format Journal Article
LanguageEnglish
Published United States 29.03.1989
Subjects
400702 - Radiochemistry & Nuclear Chemistry- Properties of Radioactive Materials
ACTINIDE COMPOUNDS
COUPLING
DATA
ELECTRONIC STRUCTURE
FIELD THEORIES
FUNCTIONS
GENERAL RELATIVITY THEORY
INFORMATION
INTERMEDIATE COUPLING
L-S COUPLING
LIGANDS
MECHANICS
NUMERICAL DATA
ORGANIC COMPOUNDS
QUANTUM MECHANICS
RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
RELATIVITY THEORY
SPECTRA
THEORETICAL DATA
URANIUM COMPOUNDS
VISIBLE SPECTRA
WAVE FUNCTIONS
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Summary:The wave functions and energy levels for uranocene, U(C{sub 8}H{sub 8}){sub 2}, have been computed using ab initio techniques including the spin-orbit interaction and relativistic core potentials. The results give detailed information on the bonding in the ground state and on the assignment of the visible spectrum. A large amount of mixing of the ligand {pi} orbitals with the uranium 6d (and 5f) orbitals was found, confirming expectations of sizable covalent bonding. The symmetry of the ground state was found to be E{sub 3g}, in agreement with some previous experimental and theoretical results. There are many low-lying 5f{sup 2} excited states, only two of which have been observed, as well as 5f {yields} 6d, {pi} {yields} 6d, and {pi} {yields} 5f excited states. The visible bands, which give uranocene its green color, previously thought to be ligand-to-metal bands, are found to be primarily due to 5f {yields} 6d excitations. The basis set of 208 generally contracted Gaussian symmetry orbitals is of slightly better than double-{xi} quality, and 32 carbon core electrons and 78 uranium core electrons were replaced by relativistic core potentials. Double-group symmetry-adapted configuration-interaction expansions up to 31,000 in length were used. Spin-orbit matrix elements were included in the Hamiltonian matrices.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja00189a022