Ab initio quantum chemical study on charge distribution and molecular structure of uranyl (VI) species with Raman frequency

Ab initio molecular orbital calculation was performed for uranyl (VI) monomer and dimer complexes with some water molecules and/or hydroxide ions. The Raman active frequencies were calculated for each complex after structural optimization in vacuum state, and investigated the molecular structure and the charge distribution. For uranyl monomer, the calculated Raman frequencies for uranyl with 5 or 6 water molecules show good agreement with experimental Raman frequencies for uranyl hydrates. On the contrary, the calculation underestimates the Raman frequency in case of hydroxide ions in uranyl complex. The calculation models for uranyl dimer were made from [UO2(H2O)(5)](2+), then the hydroxide ions bridging model, [(UO2)(2)(OH)(2)(H2O)(6)](2+), is more stable than water molecules bridging, [(UO2)(2)(H2O)(8)](4+), and the theoretical Raman frequency and uranyl bond lengths have the good coincidence with those of experiments. The calculated uranyl bond length of dimer is slightly longer than that of monomer. Also, the charge of oxygen atom in uranyl shows larger change than that of uranium atom between dimer and monomer. And this charge distribution is mostly influenced by the charge donation of ligands. If only same ligands are surrounding, the number of ligands influenced this charge distribution.