TY - JOUR
T1 - Electronic and Geometric Effects on Chemical Reactivity of 3d-Transition-Metal-Doped Silver Cluster Cations toward Oxygen Molecules
AU - Sarugaku, Shun
AU - Arakawa, Masashi
AU - Kawano, Tomoki
AU - Terasaki, Akira
N1 - Funding Information:
This work was supported by Grant for Basic Science Research Projects from the Sumitomo Foundation and Grants-in-Aid for Scientific Research (A) (JP23245006 and JP18H03901), for Scientific Research (C) (JP19K05185), and for Young Scientists (B) (JP26870431) from the Japan Society for Promotion of Science (JSPS), and for Scientific Research on Innovative Areas (JP17H06456) from the Ministry of Education Culture, Sports, Science and Technology (MEXT). The computational work was carried out by the computer facilities at Research Institute for Information Technology, Kyushu University.
Publisher Copyright:
Copyright © 2019 American Chemical Society.
PY - 2019/10/24
Y1 - 2019/10/24
N2 - 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.
AB - 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.
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U2 - 10.1021/acs.jpcc.9b05117
DO - 10.1021/acs.jpcc.9b05117
M3 - Article
AN - SCOPUS:85073467894
VL - 123
SP - 25890
EP - 25897
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
SN - 1932-7447
IS - 42
ER -