Spin Accommodation and Reactivity of Silver Clusters with Oxygen: The Enhanced Stability of Ag13鈥?/sup>

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• 作者：Zhixun Luo ; Gabriel U. Gamboa ; Jordan C. Smith ; Arthur C. Reber ; J. Ulises Reveles ; Shiv N. Khanna ; A. W. Castleman ; Jr.
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：November 21, 2012
• 年：2012
• 卷：134
• 期：46
• 页码：18973-18978
• 全文大小：402K
• 年卷期：v.134,no.46(November 21, 2012)
• ISSN：1520-5126

文摘

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鈥揺ven selective behavior is correlated with the excitation needed to activate the O鈥揙 bond in Oub>2ub>. Furthermore, by comparison with the reactivity of proximate even-electron clusters, we demonstrate that the inactivity of Agub>13ub>up>鈥?/sup> 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.