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

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32 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 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.

Original languageEnglish
Pages (from-to)3674-3679
Number of pages6
JournalJournal of Physical Chemistry C
Volume117
Issue number7
DOIs
Publication statusPublished - 2013 Feb 21
Externally publishedYes

ASJC Scopus subject areas

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

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