title: Approaching actinide(+III) hydration from first principles.
abstract: A systematic computational approach to An(III) hydration on a density-functional level of theory, using quasi-relativistic 5f-in-core pseudopotentials and valence-only basis sets for the An(III) subsystems, is presented. Molecular structures, binding energies, hydration energies, and Gibbs free energies of hydration have been calculated for [An(III)(OH(2))(h)](3+) (h = 7, 8, 9) and [An(III)(OH(2))(h-1) * OH(2)](3+) (h = 8, 9), using large (7s6p5d2f1g)/[6s5p4d2f1g] An(III) and cc-pVQZ O and H basis sets within the COSMO implicit solvation model. An(III) preferred primary hydration numbers are found to be 8 for all An(III) at the gradient-corrected density-functional level of theory. Second-order Møller-Plesset perturbation theory predicts preferred primary hydration numbers of 9 and 8 for Ac(III)-Md(III) and No(III)-Lr(III), respectively.
authors.affiliation: Institute for Theoretical Chemistry, Universität zu Köln, Greinstr. 4, D-50939 Cologne, Germany.
authors.forename: J
authors.initials: J
authors.lastname: Wiebke
authors.forename: A
authors.initials: A
authors.lastname: Moritz
authors.forename: X
authors.initials: X
authors.lastname: Cao
authors.forename: M
authors.initials: M
authors.lastname: Dolg
mesh_terms: D008671:Actinoid Series Elements / Q000737:chemistry*; D003198:Computer Simulation; D008956:Models, Chemical; D008958:Models, Molecular; D014867:Water / Q000737:chemistry*
chemical_list: D008671:Actinoid Series Elements; D014867:Water