title: Spin accommodation and reactivity of silver clusters with oxygen: the enhanced stability of Ag13(-).
abstract: Spin accommodation is demonstrated to play a determining role in the reactivity of silver cluster anions with oxygen. Odd-electron silver clusters are found to be especially reactive, while the anionic 13-atom cluster exhibits unexpected stability against reactivity with oxygen. Theoretical studies show that the odd-even selective behavior is correlated with the excitation needed to activate the O-O bond in O(2). Furthermore, by comparison with the reactivity of proximate even-electron clusters, we demonstrate that the inactivity of Ag(13)(-) is associated with its large spin excitation energy, ascribed to a crystal-field-like splitting of the orbitals caused by the bilayer atomic structure, which induces a large gap despite not having a magic number of valence electrons.
authors.affiliation: Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, USA.
authors.forename: Zhixun
authors.initials: Z
authors.lastname: Luo
authors.forename: Gabriel U
authors.initials: GU
authors.lastname: Gamboa
authors.forename: Jordan C
authors.initials: JC
authors.lastname: Smith
authors.forename: Arthur C
authors.initials: AC
authors.lastname: Reber
authors.forename: J Ulises
authors.initials: JU
authors.lastname: Reveles
authors.forename: Shiv N
authors.initials: SN
authors.lastname: Khanna
authors.forename: A W
authors.initials: AW
authors.lastname: Castleman