Analysis of Electronic States and Energy Level Structure of Uranyl in Compounds

An effective operator Hamiltonian has been developed for evaluating the excited states of uranyl ion in compounds. Including free-ion and crystal-field interactions, the parametrized Hamiltonian is able to reproduce the energy level structure in good agreement with experimental measurements on urany...

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Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2011-11, Vol.115 (44), p.12419-12425
Main Author: Liu, G. K
Format: Article
Language:English
Subjects:
A: Molecular Structure, Quantum Chemistry, General Theory
Chlorides
Coulomb friction
Energy levels
Exchange
Excitation
Mathematical analysis
Physical chemistry
Splitting
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Summary:An effective operator Hamiltonian has been developed for evaluating the excited states of uranyl ion in compounds. Including free-ion and crystal-field interactions, the parametrized Hamiltonian is able to reproduce the energy level structure in good agreement with experimental measurements on uranyl in chloride compounds and nitride complexes. It is shown that the low-lying excited states belong to a nonbonding σf configuration (therefore, one Slater integral of G3 is sufficient to account for the Coulomb electron exchange interaction) and that the spin–orbit coupling surpasses the electrostatic interactions in energy level splitting. In comparison with previously reported ab initio calculations, the present studies find that the Coulomb interactions in uranyl were excessively evaluated in the first-principle calculations.
ISSN:1089-5639
1520-5215
DOI:10.1021/jp208012q