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Gas-Phase Chemistry of Actinides Ions: New Insights into the Reaction of UO+ and UO2+ with Water
journal contribution
posted on 2007-04-11, 00:00 authored by Maria del Carmen Michelini, Nino Russo, Emilia SiciliaThe ability of uranium monoxide cations, UO+ and UO2+, to activate the O−H bond of H2O was
studied by using two different approaches of the density functional theory. First, relativistic small-core
pseudopotentials were used together with B3LYP hybrid functional. In addition, frozen-core PW91−PW91
calculations were performed within the ZORA approximation. A close description of the reaction mechanisms
leading to two different reaction products is presented, including all the involved minima and transition
states. Different possible spin states were considered as well as the effect of spin−orbit interactions on
the transition state barrier heights. The nature of the chemical bonding of the key minima and transition
states was studied by using topological methodologies (ELF, AIM). The obtained results are compared
with experimental data, as well as with previous studies on the reaction of the bare uranium cations with
water, to analyze the influence of the oxo-ligand in reactivity.