Size and structure dependence of electronic states in thiolate-protected gold nanoclusters of Au25(SR)18, Au38(SR) 24, and Au144(SR)60

Tsutomu Ohta; Masahiro Shibuta; Hironori Tsunoyama; Yuichi Negishi; Toyoaki Eguchi; Atsushi Nakajima

doi:10.1021/jp400785f

Size and structure dependence of electronic states in thiolate-protected gold nanoclusters of Au₂₅(SR)₁₈, Au₃₈(SR) ₂₄, and Au₁₄₄(SR)₆₀

Tsutomu Ohta, Masahiro Shibuta, Hironori Tsunoyama, Yuichi Negishi, Toyoaki Eguchi, Atsushi Nakajima

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

48 Citations (Scopus)

Abstract

The electronic states of three different sizes of compositionally precise thiolate-protected gold nanoclusters, Au₂₅(SR)₁₈, Au ₃₈(SR)₂₄, and Au₁₄₄(SR)₆₀ (R = C₁₂H₂₅), have been evaluated by X-ray photoemission spectroscopy. The Au 4f core-levels of the nanoclusters are well reproduced by two spectral components derived from centered core-Au and positively charged shell-Au atoms, the numbers of which are determined based on the atomic structures of the nanoclusters. The spin-orbit splitting of Au 5d_5/2 and 5d_3/2 in the valence band becomes narrower than that for bulk Au, depending on the cluster size, which is quantitatively characterized by a reduction in the average coordination number of Au. The Au 5d valence-band spectra also show that the charge reorganization of 5d electrons induced by interaction with thiol molecules is more significant for the 5d_5/2 than the 5d_3/2 orbital.

Original language	English
Pages (from-to)	3674-3679
Number of pages	6
Journal	Journal of Physical Chemistry C
Volume	117
Issue number	7
DOIs	https://doi.org/10.1021/jp400785f
Publication status	Published - 2013 Feb 21

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
Energy(all)
Physical and Theoretical Chemistry
Surfaces, Coatings and Films

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title = "Size and structure dependence of electronic states in thiolate-protected gold nanoclusters of Au25(SR)18, Au38(SR) 24, and Au144(SR)60",

abstract = "The electronic states of three different sizes of compositionally precise thiolate-protected gold nanoclusters, Au25(SR)18, Au 38(SR)24, and Au144(SR)60 (R = C12H25), have been evaluated by X-ray photoemission spectroscopy. The Au 4f core-levels of the nanoclusters are well reproduced by two spectral components derived from centered core-Au and positively charged shell-Au atoms, the numbers of which are determined based on the atomic structures of the nanoclusters. The spin-orbit splitting of Au 5d5/2 and 5d3/2 in the valence band becomes narrower than that for bulk Au, depending on the cluster size, which is quantitatively characterized by a reduction in the average coordination number of Au. The Au 5d valence-band spectra also show that the charge reorganization of 5d electrons induced by interaction with thiol molecules is more significant for the 5d5/2 than the 5d3/2 orbital.",

author = "Tsutomu Ohta and Masahiro Shibuta and Hironori Tsunoyama and Yuichi Negishi and Toyoaki Eguchi and Atsushi Nakajima",

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T1 - Size and structure dependence of electronic states in thiolate-protected gold nanoclusters of Au25(SR)18, Au38(SR) 24, and Au144(SR)60

AU - Ohta, Tsutomu

AU - Shibuta, Masahiro

AU - Tsunoyama, Hironori

AU - Negishi, Yuichi

AU - Eguchi, Toyoaki

AU - Nakajima, Atsushi

PY - 2013/2/21

Y1 - 2013/2/21

N2 - The electronic states of three different sizes of compositionally precise thiolate-protected gold nanoclusters, Au25(SR)18, Au 38(SR)24, and Au144(SR)60 (R = C12H25), have been evaluated by X-ray photoemission spectroscopy. The Au 4f core-levels of the nanoclusters are well reproduced by two spectral components derived from centered core-Au and positively charged shell-Au atoms, the numbers of which are determined based on the atomic structures of the nanoclusters. The spin-orbit splitting of Au 5d5/2 and 5d3/2 in the valence band becomes narrower than that for bulk Au, depending on the cluster size, which is quantitatively characterized by a reduction in the average coordination number of Au. The Au 5d valence-band spectra also show that the charge reorganization of 5d electrons induced by interaction with thiol molecules is more significant for the 5d5/2 than the 5d3/2 orbital.

AB - The electronic states of three different sizes of compositionally precise thiolate-protected gold nanoclusters, Au25(SR)18, Au 38(SR)24, and Au144(SR)60 (R = C12H25), have been evaluated by X-ray photoemission spectroscopy. The Au 4f core-levels of the nanoclusters are well reproduced by two spectral components derived from centered core-Au and positively charged shell-Au atoms, the numbers of which are determined based on the atomic structures of the nanoclusters. The spin-orbit splitting of Au 5d5/2 and 5d3/2 in the valence band becomes narrower than that for bulk Au, depending on the cluster size, which is quantitatively characterized by a reduction in the average coordination number of Au. The Au 5d valence-band spectra also show that the charge reorganization of 5d electrons induced by interaction with thiol molecules is more significant for the 5d5/2 than the 5d3/2 orbital.

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Size and structure dependence of electronic states in thiolate-protected gold nanoclusters of Au₂₅(SR)₁₈, Au₃₈(SR) ₂₄, and Au₁₄₄(SR)₆₀

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