Electronic and Geometric Effects on Chemical Reactivity of 3d-Transition-Metal-Doped Silver Cluster Cations toward Oxygen Molecules

Shun Sarugaku, Masashi Arakawa, Tomoki Kawano, Akira Terasaki

研究成果: Contribution to journalArticle査読

4 被引用数 (Scopus)

抄録

We report electronic and geometric structures of 3d-transition-metal-doped silver cluster cations, AgN-1M+ (M = Sc-Ni), studied by chemical reaction with oxygen molecules. The evaluated reaction rate coefficients for small sizes, N, are 2-6 orders of magnitude higher than those of undoped AgN +, whereas those for large N are comparable with those of AgN +. The low reactivity at large sizes is attributed to a geometric effect, that is, encapsulation of the dopant atom, which provides an active site located on the surface of the cluster in small sizes. In addition, a reactivity minimum is observed for AgN-1M+ with M = Sc, Ti, V, Fe, Co, and Ni at a specific size, where the cluster possesses 18 valence electrons including 3d electrons. With the aid of density functional theory calculations, the reactivity minimum is suggested to be due to an electronic effect, that is, formation of a closed electronic shell by the 18 valence electrons, implying delocalized 3d electrons. Ag13Cr+ and Ag12Mn+, possessing 18 valence electrons as well, are noted to be exceptions, where d electrons are supposed to be localized on the dopant atom because of the half-filled nature of Cr and Mn 3d orbital.

本文言語英語
ページ(範囲)25890-25897
ページ数8
ジャーナルJournal of Physical Chemistry C
123
42
DOI
出版ステータス出版済み - 10 24 2019

All Science Journal Classification (ASJC) codes

  • 電子材料、光学材料、および磁性材料
  • エネルギー(全般)
  • 物理化学および理論化学
  • 表面、皮膜および薄膜

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