title: Electronic structure and reactivity of a biradical cluster: Sc3O6(-).
abstract: The Sc(3)O(6)(-) cluster anions were produced by laser ablation and studied by reaction with n-butane in a fast flow reactor and by photoelectron spectroscopy. The reactivity experiments indicated that one Sc(3)O(6)(-) cluster can activate two n-butane molecules consecutively with rate constants on the order of 10(-10) cm(3) molecule(-1) s(-1) under near room-temperature conditions, suggesting that the even-electron system Sc(3)O(6)(-) has a highly reactive electronic structure. The photoelectron spectroscopy determined a high vertical detachment energy (VDE) of 5.63 ± 0.08 eV for the Sc(3)O(6)(-) cluster. Density functional computations indicated that the lowest energy isomer of Sc(3)O(6)(-) is an oxygen-centered biradical with a high VDE and is highly reactive toward n-butane, which is in good agreement with the experiments. The Sc(3)O(6)(-) cluster may serve as an ideal model system to provide insight into the real-life chemistry involved with the coupled O(-)˙···O(-)˙ dimers over the surfaces of metal oxide catalysts.
authors.affiliation: Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, People's Republic of China.
authors.forename: Yan-Xia
authors.initials: YX
authors.lastname: Zhao
authors.forename: Jin-Yun
authors.initials: JY
authors.lastname: Yuan
authors.forename: Xun-Lei
authors.initials: XL
authors.lastname: Ding
authors.forename: Sheng-Gui
authors.initials: SG
authors.lastname: He
authors.forename: Wei-Jun
authors.initials: WJ
authors.lastname: Zheng
mesh_terms: D000838:Anions / Q000737:chemistry*; D002073:Butanes / Q000737:chemistry*; D004583:Electrons; D008958:Models, Molecular; D056951:Photoelectron Spectroscopy; D011789:Quantum Theory; D012538:Scandium / Q000737:chemistry*
chemical_list: D000838:Anions; D002073:Butanes; C046888:butane; C046254:scandium oxide; D012538:Scandium