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Systematic theoretical investigation of structures, stabilities, and electronic properties of rhodium-doped silicon clusters: Rh2Si q n (n = 1–10; q = 0, ±1)

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Abstract

A systematic investigation of rhodium-doped silicon clusters, Rh2Si q n with n = 1–10 and q = 0, ±1, in the neutral, anionic, and cationic states is performed using density functional theory approach at B3LYP/GENECP level. According to the optimum Rh2Si q n clusters, mostly equilibrium geometries prefer the three-dimensional structures for n = 2–10. When n = 10, one Rh atom in Rh2Si 0,±110 clusters completely falls into the center of Si frame, and cage-like Rh2Si 0,±110 geometries are formed. The Rh2Si +1,6–9 and Rh2Si −5,7,9 clusters significantly deform their corresponding neutral geometries, which are in line with the calculated ionization potential and electron affinity values. The relative stabilities of Rh2Si q n clusters for the lowest-energy structures are analyzed on the basis of binding energy, fragmentation energy, second-order energy difference, and HOMO–LUMO gaps. The theoretical results confirm that the Rh2Si6 −, Rh2Si6, and Rh2Si6 + clusters are more stable than their neighboring ones. The natural population analysis reveals that the charges in Rh2Si q n clusters transfer from the Si atoms to the Rh atoms except Rh2Si+. In addition, the relationship between static polarizability and HOMO–LUMO gaps is discussed.

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Acknowledgements

This work is supported by the National Natural Science Foundation of China (Nos. 11304167 and 61306007), 973 Program of China (2014CB660804), Postdoctoral Science Foundation of China (Nos. 20110491317 and 2014T70280), Program for Science & Technology Innovation Talents in Universities of Henan Province (No. 15HASTIT020), Open Project of State Key Laboratory of Superhard Materials (No. 201405), and Young Core Instructor Foundation of Henan Province (No. 2012GGJS-152).

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  1. Department of Physics, Nanyang Normal University, Nanyang, 473061, China

    Shuai Zhang, Yu Zhang, Xingqiang Yang, Cheng Lu, Genquan Li & Zhiwen Lu

  2. State Key Laboratory of Superhard Materials, Jilin University, Changchun, 130012, China

    Cheng Lu

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Zhang, S., Zhang, Y., Yang, X. et al. Systematic theoretical investigation of structures, stabilities, and electronic properties of rhodium-doped silicon clusters: Rh2Si q n (n = 1–10; q = 0, ±1). J Mater Sci 50, 6180–6196 (2015). https://doi.org/10.1007/s10853-015-9175-x

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