Title: Intriguing structures and magic sizes of heavy noble metal nanoclusters around size 55 governed by relativistic effect and covalent bonding

Abstract

Nanoclusters usually display exotic physical and chemical properties due to their intriguing geometric structures in contrast to their bulk counterparts. By means of first-principles calculations within density functional theory, we find that heavy noble metal Pt_N nanoclusters around the size N = 55 begin to prefer an open configuration, rather than previously reported close-packed icosahedron or core-shell structures. Particularly, for Pt_N, the widely supposed icosahedronal magic cluster is changed to a three-atomic-layered structure with D_6h symmetry, which can be well addressed by our recently established generalized Wulff construction principle (GWCP). But, the magic number of Pt_N clusters around 55 is shifted to a new odd number of 57. The high symmetric three-layered Pt-57 motif is mainly stabilized by the enhanced covalent bonding contributed by both spin-orbital coupling effect and the open d orbital (5d⁹6s¹) of Pt, which result in a delicate balance between the enhanced Pt-Pt covalent bonding of the interlayers and negligible d dangling bonds on the cluster edges. Our findings about Pt_N clusters are also applicable to Ir_N clusters, but qualitatively different from their earlier neighboring element Os and their later neighboring element Au. The magic numbers for Os and Au are even, being 56 and 58, respectively.more » Finally, the findings of the new odd magic number 57 are the important supplementary of the recently established GWCP.« less

Authors:

Zhao, X. J. ^[1]; Xue, X. L. ^[1]; Guo, Z. X. ^[2]; Jia, Yu ^[3]; Li, S. F.  ^[4];

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Zhang, Zhenyu ^[5]; Gao, Y. F. ^[6]

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+ Show Author Affiliations

1. Zhengzhou Univ. (China). International Lab. for Quantum Functional Materials of Henan and School of Physics and Engineering
2. Zhengzhou Univ. (China). International Lab. for Quantum Functional Materials of Henan and School of Physics and Engineering; Univ. of College, London (United Kingdom). Dept. of Chemistry and London Centre for Nanotechnology
3. International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou 450001, China
4. Zhengzhou Univ. (China). International Lab. for Quantum Functional Materials of Henan and School of Physics and Engineering; Univ. of Science and Technology of China, Hefei (China). Hefei National Lab. for Physical Sciences at the Microscale
5. Univ. of Science and Technology of China, Hefei (China). Hefei National Lab. for Physical Sciences at the Microscale and Synergetic Innovation Center of Quantum Information and Quantum Physics
6. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Materials Science and Engineering; ; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division

Publication Date:

Mon Nov 02 00:00:00 EST 2015

Research Org.:

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:

USDOE; National Science Foundation (NSF)

OSTI Identifier:

1324152

DOE Contract Number:  

AC05-00OR22725

Resource Type:

Journal Article

Journal Name:

Journal of Chemical Physics

Additional Journal Information:

Journal Volume: 143; Journal Issue: 17; Journal ID: ISSN 0021-9606

Publisher:

American Institute of Physics (AIP)

Country of Publication:

United States

Language:

English

Subject:

36 MATERIALS SCIENCE