title: Structures and Properties of the Products of the Reaction of Lanthanide Atoms with H2O: Dominance of the +II Oxidation State.
abstract: The reactions of lanthanides with H2O have been studied using density functional theory with the B3LYP functional. H2O forms an initial Lewis acid-base complex with the lanthanides exothermically with interaction energies from -2 to -20 kcal/mol. For most of the Ln, formation of HLnOH is more exothermic than formation of H2LnO, HLnO + H, and LnOH + H. The reactions to produce HLnOH are exothermic from -25 to -75 kcal/mol. The formation of LnO + H2 for La and Ce is slightly more exothermic than formation of HLnOH and is less or equally exothermic for the rest of the lanthanides. The Ln in HLnOH and LnOH are in the formal +II and +I oxidation states, respectively. The Ln in H2LnO is mostly in the +III formal oxidation state with either Ln-O(-)/Ln-H(-) or Ln-(H2)(-)/Ln=O(2-) bonding interactions. A few of the H2LnO have the Ln in the +IV or mixed +III/+IV formal oxidation states with Ln=O(2-)/Ln-H(-) bonding interactions. The Ln in HLnO are generally in the +III oxidation state with the exception of Yb in the +II state. The orbital populations calculated within the natural bond orbital (NBO) analysis are consistent with the oxidation states and reaction energies. The more exothermic reactions to produce HLnOH are always associated with more backbonding from the O(H) and H characterized by more population in the 6s and 5d in Ln and the formation of a stronger Ln-O(H) bond. Overall, the calculations are consistent with the experiments in terms of reaction energies and vibrational frequencies.
authors.affiliation: Department of Chemistry, The University of Alabama , Shelby Hall, Tuscaloosa, Alabama 35487-0336, United States.
authors.forename: Tanya C
authors.initials: TC
authors.lastname: Mikulas
authors.affiliation: Department of Chemistry, The University of Alabama , Shelby Hall, Tuscaloosa, Alabama 35487-0336, United States.|National Center for Computational Sciences, Oak Ridge National Laboratory , Oak Ridge, Tennessee 37831, United States.
authors.forename: Mingyang
authors.initials: M
authors.lastname: Chen
authors.affiliation: Department of Chemistry, The University of Alabama , Shelby Hall, Tuscaloosa, Alabama 35487-0336, United States.
authors.forename: Zongtang
authors.initials: Z
authors.lastname: Fang
authors.affiliation: Department of Chemistry, Washington State University , Pullman, Washington 99164-4630, United States.
authors.forename: Kirk A
authors.initials: KA
authors.lastname: Peterson
authors.affiliation: Department of Chemistry, University of Virginia , Charlottesville, Virginia 22904-4319, United States.
authors.forename: Lester
authors.initials: L
authors.lastname: Andrews
authors.affiliation: Department of Chemistry, The University of Alabama , Shelby Hall, Tuscaloosa, Alabama 35487-0336, United States.
authors.forename: David A
authors.initials: DA
authors.lastname: Dixon