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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 (5d 96s 1) 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 andmore » Au are even, being 56 and 58, respectively. Finally, the findings of the new odd magic number 57 are the important supplementary of the recently established GWCP.« less

Authors:
 [1];  [1];  [2];  [3]; ORCiD logo [4];  [5];  [6]
  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:
Research Org.:
Oak Ridge National Lab. (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

Citation Formats

Zhao, X. J., Xue, X. L., Guo, Z. X., Jia, Yu, Li, S. F., Zhang, Zhenyu, and Gao, Y. F. Intriguing structures and magic sizes of heavy noble metal nanoclusters around size 55 governed by relativistic effect and covalent bonding. United States: N. p., 2015. Web. doi:10.1063/1.4934798.
Zhao, X. J., Xue, X. L., Guo, Z. X., Jia, Yu, Li, S. F., Zhang, Zhenyu, & Gao, Y. F. Intriguing structures and magic sizes of heavy noble metal nanoclusters around size 55 governed by relativistic effect and covalent bonding. United States. doi:10.1063/1.4934798.
Zhao, X. J., Xue, X. L., Guo, Z. X., Jia, Yu, Li, S. F., Zhang, Zhenyu, and Gao, Y. F. Mon . "Intriguing structures and magic sizes of heavy noble metal nanoclusters around size 55 governed by relativistic effect and covalent bonding". United States. doi:10.1063/1.4934798. https://www.osti.gov/servlets/purl/1324152.
@article{osti_1324152,
title = {Intriguing structures and magic sizes of heavy noble metal nanoclusters around size 55 governed by relativistic effect and covalent bonding},
author = {Zhao, X. J. and Xue, X. L. and Guo, Z. X. and Jia, Yu and Li, S. F. and Zhang, Zhenyu and Gao, Y. F.},
abstractNote = {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 PtN 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 PtN, the widely supposed icosahedronal magic cluster is changed to a three-atomic-layered structure with D6h symmetry, which can be well addressed by our recently established generalized Wulff construction principle (GWCP). But, the magic number of PtN 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 PtN clusters are also applicable to IrN 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. Finally, the findings of the new odd magic number 57 are the important supplementary of the recently established GWCP.},
doi = {10.1063/1.4934798},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 17,
volume = 143,
place = {United States},
year = {2015},
month = {11}
}

Works referenced in this record:

On the Structures of 55-Atom Transition-Metal Clusters and Their Relationship to the Crystalline Bulk
journal, May 2013

  • Rapps, Thomas; Ahlrichs, Reinhart; Waldt, Eugen
  • Angewandte Chemie International Edition, Vol. 52, Issue 23
  • DOI: 10.1002/anie.201302165

CALYPSO: A method for crystal structure prediction
journal, October 2012


Evidence of hollow golden cages
journal, May 2006

  • Bulusu, S.; Li, X.; Wang, L. -S.
  • Proceedings of the National Academy of Sciences, Vol. 103, Issue 22
  • DOI: 10.1073/pnas.0600637103

Assembling crystals from clusters
journal, September 1992


Projector augmented-wave method
journal, December 1994


How “Magic” is a Magic Metal Cluster?
journal, March 1996


Studies of the water-gas-shift reaction on ceria-supported Pt, Pd, and Rh: Implications for oxygen-storage properties
journal, January 1998


Platinum Nanoparticle Shape Effects on Benzene Hydrogenation Selectivity
journal, October 2007

  • Bratlie, Kaitlin M.; Lee, Hyunjoo; Komvopoulos, Kyriakos
  • Nano Letters, Vol. 7, Issue 10
  • DOI: 10.1021/nl0716000

Electronic Shell Structure and Abundances of Sodium Clusters
journal, June 1984


C60: Buckminsterfullerene
journal, November 1985

  • Kroto, H. W.; Heath, J. R.; O'Brien, S. C.
  • Nature, Vol. 318, Issue 6042
  • DOI: 10.1038/318162a0

Fullerene-Based Carbon Nanostructures for Methanol Oxidation
journal, March 2004

  • Vinodgopal, K.; Haria, Mehul; Meisel, Dan
  • Nano Letters, Vol. 4, Issue 3
  • DOI: 10.1021/nl035028y

Electron Pairing in Ferroelectric Niobium and Niobium Alloy Clusters
journal, July 2008

  • Yin, Shuangye; Xu, Xiaoshan; Liang, Anthony
  • Journal of Superconductivity and Novel Magnetism, Vol. 21, Issue 5
  • DOI: 10.1007/s10948-008-0332-1

Covalent gold
journal, January 2010

  • Wang, Lai-Sheng
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 31
  • DOI: 10.1039/c003886e

Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995


Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994


Dual Relationship between Large Gold Clusters (Antifullerenes) and Carbon Fullerenes:  A New Lowest-Energy Cage Structure for Au 50
journal, January 2007

  • Tian, Dongxu; Zhao, Jijun; Wang, Baolin
  • The Journal of Physical Chemistry A, Vol. 111, Issue 3
  • DOI: 10.1021/jp066272r

Periodic trends in the geometric structures of 13-atom metal clusters
journal, February 2008


Crystal structure prediction via particle-swarm optimization
journal, September 2010


Inhomogeneous Electron Gas
journal, November 1964


Superconductivity at 18 K in potassium-doped C60
journal, April 1991

  • Hebard, A. F.; Rosseinsky, M. J.; Haddon, R. C.
  • Nature, Vol. 350, Issue 6319
  • DOI: 10.1038/350600a0

Alternative Low-Symmetry Structure for 13-Atom Metal Clusters
journal, September 2004


Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation
journal, September 1992


Density-functional-theory study of 13-atom metal clusters M 13 , M = Ta Pt
journal, April 2009


Controllable Pt Nanoparticle Deposition on Carbon Nanotubes as an Anode Catalyst for Direct Methanol Fuel Cells
journal, December 2005

  • Mu, Yongyan; Liang, Hanpu; Hu, Jinsong
  • The Journal of Physical Chemistry B, Vol. 109, Issue 47
  • DOI: 10.1021/jp0555448

Experimental and Theoretical Investigation of the Electronic and Geometrical Structures of the Au32 Cluster
journal, November 2005

  • Ji, Min; Gu, Xiao; Li, Xi
  • Angewandte Chemie International Edition, Vol. 44, Issue 43
  • DOI: 10.1002/anie.200502795

Relativity and the periodic system of elements
journal, August 1979

  • Pyykko, Pekka; Desclaux, Jean Paul
  • Accounts of Chemical Research, Vol. 12, Issue 8
  • DOI: 10.1021/ar50140a002

Evidence of Significant Covalent Bonding in Au(CN) 2
journal, November 2009

  • Wang, Xue-Bin; Wang, Yi-Lei; Yang, Jie
  • Journal of the American Chemical Society, Vol. 131, Issue 45
  • DOI: 10.1021/ja908106e

Density-Functional Calculations on Platinum Nanoclusters:  Pt 13 , Pt 38 , and Pt 55
journal, April 2003

  • Aprà, Edoardo; Fortunelli, Alessandro
  • The Journal of Physical Chemistry A, Vol. 107, Issue 16
  • DOI: 10.1021/jp0275793

Magic Numbers for Sphere Packings: Experimental Verification in Free Xenon Clusters
journal, October 1981


Stacking Principle and Magic Sizes of Transition Metal Nanoclusters Based on Generalized Wulff Construction
journal, September 2013


Quantum size effects in metal particles
journal, July 1986


Amorphization Mechanism of Icosahedral Metal Nanoclusters
journal, August 2004


hcp metal nanoclusters with hexagonal A A bilayer stacking stabilized by enhanced covalent bonding
journal, July 2010


Relativistic Effects and the Unique Low-Symmetry Structures of Gold Nanoclusters
journal, May 2008

  • Huang, Wei; Ji, Min; Dong, Chuan-Ding
  • ACS Nano, Vol. 2, Issue 5
  • DOI: 10.1021/nn800074b

Calcium as the Superior Coating Metal in Functionalization of Carbon Fullerenes for High-Capacity Hydrogen Storage
journal, May 2008


Rotationally resolved spectroscopy of Pt2
journal, January 2002

  • Airola, Marc B.; Morse, Michael D.
  • The Journal of Chemical Physics, Vol. 116, Issue 4
  • DOI: 10.1063/1.1428753

Identification of Active Gold Nanoclusters on Iron Oxide Supports for CO Oxidation
journal, September 2008


Symmetry and Electronic Structure of Noble-Metal Nanoparticles and the Role of Relativity
journal, August 2004


A nanometre-scale electronic switch consisting of a metal cluster and redox-addressable groups
journal, November 2000

  • Gittins, David I.; Bethell, Donald; Schiffrin, David J.
  • Nature, Vol. 408, Issue 6808
  • DOI: 10.1038/35040518

Reconstruction of core and surface nanoparticles: The example of Pt 55 and Au 55
journal, November 2010

  • Da Silva, Juarez L. F.; Kim, Hyoung Gyu; Piotrowski, Maurício J.
  • Physical Review B, Vol. 82, Issue 20
  • DOI: 10.1103/PhysRevB.82.205424

Dispersed fluorescence spectroscopy of jet-cooled AgAu and Pt2
journal, October 2001

  • Fabbi, Jacqueline C.; Langenberg, Jon D.; Costello, Quinton D.
  • The Journal of Chemical Physics, Vol. 115, Issue 16
  • DOI: 10.1063/1.1407273

Crossover among structural motifs in transition and noble-metal clusters
journal, March 2002

  • Baletto, F.; Ferrando, R.; Fortunelli, A.
  • The Journal of Chemical Physics, Vol. 116, Issue 9
  • DOI: 10.1063/1.1448484