title: Molecular Structure and Bonding in Plutonium Carbides: A Theoretical Study of PuC3.
abstract: The most relevant species of plutonium tricarbide were characterized using theoretical methods. The global minimum is predicted to be a fan structure where the plutonium atom is bonded to a quasi-linear C3 unit. A rhombic isomer, shown to be a bicyclic species with transannular C-C bonding, lies about 39 kJ/mol above the fan isomer. A linear PuCCC isomer and a three-membered ring CPuC2 isomer were found to be higher in energy (150 and 195 kJ/mol, respectively, above the predicted global minimum). The possible processes for the formation of these species are discussed, and the IR spectra were predicted to help in possible experimental detection. The nature of the Pu-C interaction has been analyzed in terms of a topological analysis of the electronic density, showing that Pu-C bonding is essentially ionic with a certain degree of covalent character.
authors.affiliation: Instituto de Estructura de la Materia, IEM-CSIC , Serrano 123, 28006 Madrid, Spain.
authors.forename: Germán
authors.initials: G
authors.lastname: Molpeceres
authors.affiliation: Departamento de Química Física y Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid , Campus Miguel Delibes, Paseo de Belén 7, 47011 Valladolid, Spain.
authors.forename: Víctor M
authors.initials: VM
authors.lastname: Rayón
authors.affiliation: Departamento de Química Física y Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid , Campus Miguel Delibes, Paseo de Belén 7, 47011 Valladolid, Spain.
authors.forename: Carmen
authors.initials: C
authors.lastname: Barrientos
authors.affiliation: Departamento de Química Física y Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid , Campus Miguel Delibes, Paseo de Belén 7, 47011 Valladolid, Spain.
authors.forename: Antonio
authors.initials: A
authors.lastname: Largo