10.1021/ja065683i.s001
Maria del Carmen Michelini
Maria
del Carmen Michelini
Nino Russo
Nino
Russo
Emilia Sicilia
Emilia
Sicilia
Gas-Phase Chemistry of Actinides Ions: New Insights into
the Reaction of UO<sup>+</sup> and UO<sup>2+</sup> with Water
American Chemical Society
2007
minima
2O
3LYP
PW
transition states
AIM
ELF
UO
transition state barrier heights
ZORA
uranium monoxide cations
2007-04-11 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Gas_Phase_Chemistry_of_Actinides_Ions_New_Insights_into_the_Reaction_of_UO_sup_sup_and_UO_sup_2_sup_with_Water/3013522
The ability of uranium monoxide cations, UO<sup>+</sup> and UO<sup>2+</sup>, to activate the O−H bond of H<sub>2</sub>O 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.