title: Evolution of the Spin Magnetic Moments and Atomic Valence of Vanadium in VCux+, VAgx+, and VAux+Clusters (x = 3-14).
abstract: The atomic structures, bonding characteristics, spin magnetic moments, and stability of VCux+, VAgx+, and VAux+(x = 3-14) clusters were examined using density functional theory. Our studies indicate that the effective valence of vanadium is size-dependent and that at small sizes some of the valence electrons of vanadium are localized on vanadium, while at larger sizes the 3d orbitals of the vanadium participate in metallic bonding eventually quenching the spin magnetic moment. The electronic stability of the clusters may be understood through a split-shell model that partitions the valence electrons in either a delocalized shell or localized on the vanadium atom. A molecular orbital analysis reveals that in planar clusters the delocalization of the 3d orbital of vanadium is enhanced when surrounded by gold due to enhanced 6s-5d hybridization. Once the clusters become three-dimensional, this hybridization is reduced, and copper most readily delocalizes the vanadium's valence electrons. By understanding these unique features, greater insight is offered into the role of a host material's electronic structure in determining the bonding characteristics and stability of localized spin magnetic moments in quantum confined systems.
authors.affiliation: Department of Physics, Virginia Commonwealth University , Richmond, Virginia 23284, United States.|Department of Materials Science and Engineering, University of Virginia , Charlottesville, Virginia 22904, United States.
authors.forename: William H
authors.initials: WH
authors.lastname: Blades
authors.affiliation: Department of Physics, Virginia Commonwealth University , Richmond, Virginia 23284, United States.
authors.forename: Arthur C
authors.identifier: http://orcid.org/0000-0003-1013-331X
authors.initials: AC
authors.lastname: Reber
authors.affiliation: Department of Physics, Virginia Commonwealth University , Richmond, Virginia 23284, United States.
authors.forename: Shiv N
authors.identifier: http://orcid.org/0000-0002-9797-1289
authors.initials: SN
authors.lastname: Khanna
authors.affiliation: Departamento de Química, CINVESTAV , Av. Instituto Politécnico Nacional 2508, A.P. 14-740, México D.F. 07000, Mexico.
authors.forename: Luis
authors.initials: L
authors.lastname: López-Sosa
authors.affiliation: Departamento de Química, CINVESTAV , Av. Instituto Politécnico Nacional 2508, A.P. 14-740, México D.F. 07000, Mexico.
authors.forename: Patrizia
authors.initials: P
authors.lastname: Calaminici
authors.affiliation: Departamento de Química, CINVESTAV , Av. Instituto Politécnico Nacional 2508, A.P. 14-740, México D.F. 07000, Mexico.
authors.forename: Andreas M
authors.initials: AM
authors.lastname: Köster