title: Born-Oppenheimer molecular dynamics studies of Pb(ii) micro hydrated gas phase clusters.
abstract: In this work, a theoretical investigation was made to assess the coordination properties of Pb(ii) in [Pb(H2O)n]2+clusters, with n = 4, 6, 8, 12, and 29, as well as to study proton transfer events, by means of Born-Oppenheimer molecular dynamics simulations at the B3LYP/aug-cc-pVDZ-pp/6-311G level of theory, that were calibrated in comparison with B3LYP/aug-cc-pVDZ-PP/aug-cc-pVDZ calculations. Hemidirected configurations were found in all cases; the radial distribution functions (RDFs) produced well defined first hydration shells (FHSs) for n = 4,6,8, and 12, that resulted in a coordination number CN = 4, whereas a clear-cut FHS was not found for n = 29 because the RDF did not have a vacant region after the first maximum; however, three water molecules remained directly interacting with the Pb ion for the whole simulation, while six others stayed at average distances shorter than 4 Å but dynamically getting closer and farther, thus producing a CN ranging from 6 to 9, depending on the criterion used to define the first hydration shell. In agreement with experimental data and previous calculations, proton transfer events were observed for n≤8 but not for n≥12. For an event to occur, a water molecule in the second hydration shell had to make a single hydrogen bond with a water molecule in the first hydration shell.
authors.affiliation: Instituto de Ciencias Físicas, Universidad Autónoma de México, Apdo. Postal 48-3, Cuernavaca, Morelos 62251, Mexico.
authors.forename: C I
authors.initials: CI
authors.lastname: León-Pimentel
authors.affiliation: Instituto de Ciencias Físicas, Universidad Autónoma de México, Apdo. Postal 48-3, Cuernavaca, Morelos 62251, Mexico.
authors.forename: J I
authors.initials: JI
authors.lastname: Amaro-Estrada
authors.affiliation: Instituto de Ciencias Físicas, Universidad Autónoma de México, Apdo. Postal 48-3, Cuernavaca, Morelos 62251, Mexico.
authors.forename: H
authors.identifier: 0000000341596165
authors.initials: H
authors.lastname: Saint-Martin
authors.affiliation: Depto. de Física, Centro de Investigación en Ciencias, IICBA. Universidad Autónoma del Estado de Morelos, Cuernavaca, Morelos 62209, Mexico.
authors.forename: A
authors.initials: A
authors.lastname: Ramírez-Solís