Hierarchy of bond stiffnesses within icosahedral-based gold clusters protected by thiolates

被引:142
作者
Yamazoe, Seiji [1 ,2 ]
Takano, Shinjiro [1 ]
Kurashige, Wataru [3 ]
Yokoyama, Toshihiko [4 ]
Nitta, Kiyofumi [5 ]
Negishi, Yuichi [3 ]
Tsukuda, Tatsuya [1 ,2 ]
机构
[1] Univ Tokyo, Sch Sci, Dept Chem, Bunkyo Ku, 7-3-1 Hongo, Tokyo 1130033, Japan
[2] Kyoto Univ, ESICB, Kyoto 6158520, Japan
[3] Tokyo Univ Sci, Fac Sci, Dept Appl Chem, Shinjuku Ku, 1-3 Kagurazaka, Tokyo 1628601, Japan
[4] Natl Inst Nat Sci, Inst Mol Sci, Dept Mat Mol Sci, 38 Nishigonaka, Okazaki, Aichi 4448585, Japan
[5] Japan Synchrotron Radiat Res Inst, SPring 8,1-1-1 Koto, Sayo, Hyogo 6795198, Japan
来源
NATURE COMMUNICATIONS | 2016年 / 7卷
关键词
VIBRATIONAL-SPECTRUM; DEBYE TEMPERATURE; THERMAL-EXPANSION; CRYSTAL-STRUCTURE; SIZE; NANOCLUSTERS; HEAT; AU;
D O I
10.1038/ncomms10414
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
Unique thermal properties of metal clusters are believed to originate from the hierarchy of the bonding. However, an atomic-level understanding of how the bond stiffnesses are affected by the atomic packing of a metal cluster and the interfacial structure with the surrounding environment has not been attained to date. Here we elucidate the hierarchy in the bond stiffness in thiolate-protected, icosahedral-based gold clusters Au-25(SC2H4Ph)(18), Au-38(SC2H4Ph)(24) and Au-144(SC2H4Ph)(60) by analysing Au L-3-edge extended X-ray absorption fine structure data. The Au-Au bonds have different stiffnesses depending on their lengths. The long Au-Au bonds, which are more flexible than those in the bulk metal, are located at the icosahedral-based gold core surface. The short Au-Au bonds, which are stiffer than those in the bulk metal, are mainly distributed along the radial direction and form a cyclic structural backbone with the rigid Au-SR oligomers.
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页数:7
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共 35 条
  • [1] Real-space multiple-scattering calculation and interpretation of x-ray-absorption near-edge structure
    Ankudinov, AL
    Ravel, B
    Rehr, JJ
    Conradson, SD
    [J]. PHYSICAL REVIEW B, 1998, 58 (12): : 7565 - 7576
  • [2] Vibrational properties of Ge nanocrystals determined by EXAFS
    Araujo, L. L.
    Kluth, P.
    Azevedo, G. de M.
    Ridgway, M. C.
    [J]. PHYSICAL REVIEW B, 2006, 74 (18)
  • [3] Particle size and interfacial effect on the specific heat of nanocrystalline Fe
    Bai, HY
    Luo, JL
    Jin, D
    Sun, JR
    [J]. JOURNAL OF APPLIED PHYSICS, 1996, 79 (01) : 361 - 364
  • [4] SIZE EFFECT ON MELTING TEMPERATURE OF GOLD PARTICLES
    BUFFAT, P
    BOREL, JP
    [J]. PHYSICAL REVIEW A, 1976, 13 (06) : 2287 - 2298
  • [5] Bonding properties of thiolate-protected gold nanoclusters and structural analogs from X-ray absorption spectroscopy
    Chevrier, Daniel M.
    Yang, Rui
    Chatt, Amares
    Zhang, Peng
    [J]. NANOTECHNOLOGY REVIEWS, 2015, 4 (02) : 193 - 206
  • [6] Melting of gold clusters: Icosahedral precursors
    Cleveland, CL
    Luedtke, WD
    Landman, U
    [J]. PHYSICAL REVIEW LETTERS, 1998, 81 (10) : 2036 - 2039
  • [7] Temperature dependence of the structural parameters of gold nanoparticles investigated with EXAFS
    Comaschi, T.
    Balerna, A.
    Mobilio, S.
    [J]. PHYSICAL REVIEW B, 2008, 77 (07):
  • [8] Nanocluster Size Evolution Studied by Mass Spectrometry in Room Temperature Au25(SR)18 Synthesis
    Dharmaratne, Asantha C.
    Krick, Thomas
    Dass, Amala
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (38) : 13604 - +
  • [9] Temperature dependence of EXAFS cumulants of Ag nanoparticles in glass
    Dubiel, M.
    Haug, J.
    Kruth, H.
    Hofmeister, H.
    Seifert, W.
    [J]. 14TH INTERNATIONAL CONFERENCE ON X-RAY ABSORPTION FINE STRUCTURE (XAFS14), PROCEEDINGS, 2009, 190
  • [10] Anomalous vibrational properties induced by surface effects in capped Pt nanoparticles
    Giovanetti, Lisandro J.
    Ramallo-Lopez, Jose M.
    Requejo, Felix G.
    Garcia-Gutierrez, Domingo I.
    Jose-Yacaman, Miguel
    Craievich, Aldo F.
    [J]. JOURNAL OF PHYSICAL CHEMISTRY C, 2007, 111 (21) : 7599 - 7604