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Title: Beyond the staple motif: a new order at the thiolate–gold interface

Abstract

Staple motifs in the form of –RS(AuSR) x– (x = 1, 2, 3, etc.) are the most common structural feature at the interface of the thiolate-protected gold nanoclusters, Au n(SR) m. However, the recently solved structure of Au 92(SR) 44, in which the facets of the Au 84 core are protected mainly by the bridging thiolates, challenges the staple hypothesis. Herein, we explore the surface sensitivity of the thiolate–gold interface from first principles density functional theory. We find that the interfacial structures of thiolates on gold are surface sensitive: while a staple motif (such as –RS–Au–SR–) is preferred on Au(111), a bridging motif (–RS–) is preferred on Au(100) and Au(110). We show that this surface sensitivity is closely related to the coordination number of the surface Au atom on the different surfaces. We further confirm the preference of the bridging motif for self-assembled monolayers of two different ligands (methylthiolate and 4-tert-butylbenzenethiolate) on Au(100). With this surface sensitivity, we categorize the structure-known Au n(SR) m clusters into three groups: (1) no bridging; (2) ambiguous bridging; (3) distinct bridging. We further employ the surface sensitivity of the thiolate–Au interface to predict the protecting motifs of face-centered cubic (fcc) gold nanoparticles of differentmore » shapes. In conclusion, our study provides a unifying view of the Au n(SR) m structures with guidelines for structure predictions for larger Au n(SR) m clusters of a fcc core.« less

Authors:
 [1];  [2];  [1]
  1. Univ. of California, Riverside, CA (United States). Dept. of Chemistry
  2. Carnegie Mellon Univ., Pittsburgh, PA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1491834
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Nanoscale
Additional Journal Information:
Journal Volume: 8; Journal Issue: 48; Journal ID: ISSN 2040-3364
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats

Hu, Guoxiang, Jin, Rongchao, and Jiang, De-en. Beyond the staple motif: a new order at the thiolate–gold interface. United States: N. p., 2016. Web. doi:10.1039/c6nr07709a.
Hu, Guoxiang, Jin, Rongchao, & Jiang, De-en. Beyond the staple motif: a new order at the thiolate–gold interface. United States. doi:10.1039/c6nr07709a.
Hu, Guoxiang, Jin, Rongchao, and Jiang, De-en. Fri . "Beyond the staple motif: a new order at the thiolate–gold interface". United States. doi:10.1039/c6nr07709a. https://www.osti.gov/servlets/purl/1491834.
@article{osti_1491834,
title = {Beyond the staple motif: a new order at the thiolate–gold interface},
author = {Hu, Guoxiang and Jin, Rongchao and Jiang, De-en},
abstractNote = {Staple motifs in the form of –RS(AuSR)x– (x = 1, 2, 3, etc.) are the most common structural feature at the interface of the thiolate-protected gold nanoclusters, Aun(SR)m. However, the recently solved structure of Au92(SR)44, in which the facets of the Au84 core are protected mainly by the bridging thiolates, challenges the staple hypothesis. Herein, we explore the surface sensitivity of the thiolate–gold interface from first principles density functional theory. We find that the interfacial structures of thiolates on gold are surface sensitive: while a staple motif (such as –RS–Au–SR–) is preferred on Au(111), a bridging motif (–RS–) is preferred on Au(100) and Au(110). We show that this surface sensitivity is closely related to the coordination number of the surface Au atom on the different surfaces. We further confirm the preference of the bridging motif for self-assembled monolayers of two different ligands (methylthiolate and 4-tert-butylbenzenethiolate) on Au(100). With this surface sensitivity, we categorize the structure-known Aun(SR)m clusters into three groups: (1) no bridging; (2) ambiguous bridging; (3) distinct bridging. We further employ the surface sensitivity of the thiolate–Au interface to predict the protecting motifs of face-centered cubic (fcc) gold nanoparticles of different shapes. In conclusion, our study provides a unifying view of the Aun(SR)m structures with guidelines for structure predictions for larger Aun(SR)m clusters of a fcc core.},
doi = {10.1039/c6nr07709a},
journal = {Nanoscale},
number = 48,
volume = 8,
place = {United States},
year = {2016},
month = {11}
}

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Works referenced in this record:

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