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Structure and Bonding Properties of a 20-Gold-Atom Nanocluster Studied by Theoretical X-ray Absorption Spectroscopy

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Abstract

Gold nanoclusters with precisely controlled atomic composition have emerged as promising materials for applications in nanotechnology because of their unique optical, electronic and catalytic properties. The recent discovery of a 20-gold-atom nanocluster protected by 16 organothiolate molecules, Au20(SR)16, is the smallest member in a surprising series of small gold−thiolate nanoclusters with a face-centered cubic (FCC) ordered core structures. A fundamental challenge facing gold nanocluster research is being able to understand the composition-dependent properties from a site-specific perspective in order to confidently establish structure-property relationships. A step in this direction is to examine the influence of various structural features (core geometry and thiolate-gold bonding motifs) on the bonding properties of gold-thiolate nanoclusters. In this work, ab initio simulations were conducted to systematically study the local structure and electronic properties of Au20(SR)16 from each unique Au and S atomic site using Au L3-edge extended X-ray absorption fine structure (EXAFS), projected density of states (l-DOS) and S K-edge X-ray absorption near edge structure (XANES) spectra. Two larger FCC-like gold-thiolate nanoclusters (Au28(SR)20 and Au36(SR)24) were used for a comparative study with Au20(SR)16, providing further predictions about the cluster size effect on the bonding properties of gold-thiolate nanoclusters with FCC-like core structures. Through this comparison, the smaller core size of Au20(SR)16 produces an EXAFS scattering signature that is non-FCC-like but shows very similar electronic properties with a larger FCC-like gold-thiolate nanocluster.

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Authors and Affiliations

  1. Department of Chemistry, Dalhousie University, Halifax, NS, B3H 4R2, USA

    Rui Yang, Daniel M. Chevrier & Peng Zhang

  2. Department of Chemistry and School of Biomedical Engineering, Dalhousie University, Halifax, NS, B3H 4R2, USA

    Peng Zhang

Authors
  1. Rui Yang
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  2. Daniel M. Chevrier
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  3. Peng Zhang
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Correspondence to Peng Zhang.

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Yang, R., Chevrier, D.M. & Zhang, P. Structure and Bonding Properties of a 20-Gold-Atom Nanocluster Studied by Theoretical X-ray Absorption Spectroscopy. MRS Online Proceedings Library 1802, 5 (2015). https://doi.org/10.1557/opl.2015.516

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