Title: Electronic spectrum of UO22+ and [UO2Cl4](2-) calculated with time-dependent density functional theory
Authors: Pierloot, Kristine ×
van Besien, Els
van Lenthe, Erik
Baerends, Evert Jan #
Issue Date: May-2007
Publisher: Amer inst physics
Series Title: Journal of Chemical Physics vol:126 issue:19 pages:194311
Abstract: The electronic spectra of UO22+ and [UO2Cl4](2-) are calculated with a recently proposed relativistic time-dependent density functional theory method based on the two-component zeroth-order regular approximation for the inclusion of spin-orbit coupling and a noncollinear exchange-correlation functional. All excitations out of the bonding sigma(+)(u) orbital into the nonbonding delta(u) or phi(u) orbitals for UO22+ and the corresponding excitations for [UO2Cl4](2-) are considered. Scalar relativistic vertical excitation energies are compared to values from previous calculations with the CASPT2 method. Two-component adiabatic excitation energies, U-O equilibrium distances, and symmetric stretching frequencies are compared to CASPT2 and combined configuration-interaction and spin-orbit coupling results, as well as to experimental data. The composition of the excited states in terms of the spin-orbit free states is analyzed. The results point to a significant effect of the chlorine ligands on the electronic spectrum, thereby confirming the CASPT2 results: The excitation energies are shifted and a different luminescent state is found. (C) 2007 American Institute of Physics.
ISSN: 0021-9606
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Quantum Chemistry and Physical Chemistry Section
× corresponding author
# (joint) last author

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