Chemical analysis of the superatom model for sulfur-stabilized gold nanoparticles

Reimers, JR; Wang, Y; Cankurtaran, BO; Ford, MJ

Chemical analysis of the superatom model for sulfur-stabilized gold nanoparticles

Reimers, JR

Wang, Y

Cankurtaran, BO Ford, MJ

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Publication Type:: Journal Article
Citation:: Journal of the American Chemical Society, 2010, 132 (24), pp. 8378 - 8384
Issue Date:: 2010-06-23

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Field	Value	Language
dc.contributor.author	Reimers, JR https://orcid.org/0000-0001-5157-7422	en_US
dc.contributor.author	Wang, Y https://orcid.org/0000-0001-8619-0455	en_US
dc.contributor.author	Cankurtaran, BO	en_US
dc.contributor.author	Ford, MJ https://orcid.org/0000-0002-8595-5900	en_US
dc.date.issued	2010-06-23	en_US
dc.identifier.citation	Journal of the American Chemical Society, 2010, 132 (24), pp. 8378 - 8384	en_US
dc.identifier.issn	0002-7863	en_US
dc.identifier.uri	http://hdl.handle.net/10453/13139
dc.description.abstract	The superatom model for nanoparticle structure is shown to be inadequate for the prediction of the thermodynamic stability of gold nanoparticles. The observed large HOMO-LUMO gaps for stable nanoparticles predicted by this model are, for sulfur-stabilized gold nanoparticles, attributed to covalent interactions of the metal with thiyl adsorbate radicals rather than ionic interactions with thiolate adsorbate ions, as is commonly presumed. In particular, gold adatoms in the stabilizing layer are shown to be of Au(0) nature, subtle but significantly different from the atoms of the gold core owing to the variations in the proportion of gold-gold and gold-sulfur links that form. These interactions explain the success of the superatom model in describing the electronic structure of both known and informatory nanoparticle compositions. Nanoparticle reaction energies are, however, found not to correlate with the completion of superatom shells. Instead, local structural effects are found to dominate the chemistry and in particular the significanctly different chemical properties of gold nanoparticle and bulk surfaces. These conclusions are drawn from density-functional-theory calculations for the Au102(p-mercaptobenzoic acid)44 nanoparticle based on the X-ray structure (Jadzinsky, P. D.; et al. Science 2007, 318, 430), as well calculations for the related Au102(S*-CH 3)44 nanoparticle, for the inner gold-cluster cores, for partially and overly reacted cores, and for Au(111) surface adsorbates. © 2010 American Chemical Society.	en_US
dc.relation.ispartof	Journal of the American Chemical Society	en_US
dc.relation.isbasedon	10.1021/ja101083v	en_US
dc.subject.classification	General Chemistry	en_US
dc.subject.mesh	Sulfur	en_US
dc.subject.mesh	Gold	en_US
dc.subject.mesh	Molecular Conformation	en_US
dc.subject.mesh	Quantum Theory	en_US
dc.subject.mesh	Thermodynamics	en_US
dc.subject.mesh	Models, Molecular	en_US
dc.subject.mesh	Metal Nanoparticles	en_US
dc.title	Chemical analysis of the superatom model for sulfur-stabilized gold nanoparticles	en_US
dc.type	Journal Article
utslib.citation.volume	24	en_US
utslib.citation.volume	132	en_US
utslib.for	039999 Chemical Sciences not elsewhere classified	en_US
utslib.for	03 Chemical Sciences	en_US
dc.location.activity	ISI:000278905700036	en_US
pubs.embargo.period	Not known	en_US
pubs.organisational-group	/University of Technology Sydney
pubs.organisational-group	/University of Technology Sydney/DVC (Research)
pubs.organisational-group	/University of Technology Sydney/Faculty of Arts and Social Sciences
pubs.organisational-group	/University of Technology Sydney/Faculty of Science
pubs.organisational-group	/University of Technology Sydney/Faculty of Science/School of Mathematical and Physical Sciences
utslib.copyright.status	open_access
pubs.issue	24	en_US
pubs.publication-status	Published	en_US
pubs.volume	132	en_US

Abstract:

The superatom model for nanoparticle structure is shown to be inadequate for the prediction of the thermodynamic stability of gold nanoparticles. The observed large HOMO-LUMO gaps for stable nanoparticles predicted by this model are, for sulfur-stabilized gold nanoparticles, attributed to covalent interactions of the metal with thiyl adsorbate radicals rather than ionic interactions with thiolate adsorbate ions, as is commonly presumed. In particular, gold adatoms in the stabilizing layer are shown to be of Au(0) nature, subtle but significantly different from the atoms of the gold core owing to the variations in the proportion of gold-gold and gold-sulfur links that form. These interactions explain the success of the superatom model in describing the electronic structure of both known and informatory nanoparticle compositions. Nanoparticle reaction energies are, however, found not to correlate with the completion of superatom shells. Instead, local structural effects are found to dominate the chemistry and in particular the significanctly different chemical properties of gold nanoparticle and bulk surfaces. These conclusions are drawn from density-functional-theory calculations for the Au102(p-mercaptobenzoic acid)44 nanoparticle based on the X-ray structure (Jadzinsky, P. D.; et al. Science 2007, 318, 430), as well calculations for the related Au102(S*-CH 3)44 nanoparticle, for the inner gold-cluster cores, for partially and overly reacted cores, and for Au(111) surface adsorbates. © 2010 American Chemical Society.

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http://hdl.handle.net/10453/13139