Electronic spectrum of UO2(2+) and [UO2Cl4]2- calculated with time-dependent density functional theory

K. Pierloot, E. van Besien, E. van Lenthe, E.J. Baerends

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The electronic spectra of U O2 2+ and [U O2 Cl4] 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 u+ orbital into the nonbonding δu or φu orbitals for U O2 2+ and the corresponding excitations for [U O2 Cl4] 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. © 2007 American Institute of Physics.
Original languageEnglish
Pages (from-to)194311
JournalJournal of Chemical Physics
Issue number19
Publication statusPublished - 2007


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