title: An ab initio theoretical study of the electronic structure of UO2(+) and [UO2(CO3)3]5-.
abstract: The electronic spectra up to 50,000 cm(-1) of uranyl(V) both as a bare ion, UO2(+), and coordinated with three carbonate ligands, [UO2(CO3)3]5-, are presented. Solvent effects were treated by a nonequilibrium continuum solvent model. The transition energies were obtained at the spin-orbit level using relativistic wave function based multiconfigurational methods such as the complete active space self-consistent field method (CASSCF)and the complete active space with second-order perturbation theory (CASPT2) followed by a calculation of the spin-orbit effects at the variation-perturbation level. Earlier relativistic intermediate Hamiltonian Fock space coupled-cluster calculations on the spectrum of the bare uranyl(V) ion were extended to investigate the influence of electron correlation effects on spacings between the electronic states. This study is an attempt to contribute to an enhanced understanding of the electronic structure of actinyl ions. Both spectra show transitions within nonbonding orbitals and between nonbonding and antibonding orbitals as well as charge transfers from the uranyl oxygens to uranium. The ground state in UO2(+) is found to be 2Φ(5/2u), corresponding to the σ(u)(2)φ(u)(1) configuration, while in [UO2(CO3)3]5-, it is 2Δ(3/2u), arising from the σ(u)(2)δ(u)(1) configuration. It is remarkable that the excited state corresponding to an excitation from the nonbonding δ(u) to the uranyl antibonding 3π(u)* molecular orbital is significantly lower in energy in the carbonate complex, 6623 cm(-1), than that in the bare ion, 17,908 cm(-1). The first ligand (carbonate) to metal charge-transfer excitation is estimated to occur above 50,000 cm(-1). The reported results compare favorably with experiment when available.
authors.affiliation: Department of Physics, Stockholm University, AlbaNova University Centre, 106 91 Stockholm, Sweden. fernando@physto.se
authors.forename: Fernando
authors.initials: F
authors.lastname: Ruipérez
authors.forename: Cécile
authors.initials: C
authors.lastname: Danilo
authors.forename: Florent
authors.initials: F
authors.lastname: Réal
authors.forename: Jean-Pierre
authors.initials: JP
authors.lastname: Flament
authors.forename: Valérie
authors.initials: V
authors.lastname: Vallet
authors.forename: Ulf
authors.initials: U
authors.lastname: Wahlgren