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Formation of Gold−Methanethiyl Self-Assembled Monolayers

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School of Chemistry and School of Molecular and Microbial Biosciences, The University of Sydney, NSW 2006, Australia
Cite this: J. Am. Chem. Soc. 2007, 129, 47, 14532–14533
Publication Date (Web):November 8, 2007
https://doi.org/10.1021/ja0743442
Copyright © 2007 American Chemical Society

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    Abstract

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    The energetics of formation of thiyl-gold self-assembled monolayers is investigated using density-functional theory simulations. It is found that the chemisorption of dimethyl disulfide on the reconstructed Au(111) (22 × √3) surface is most favored at the fcc reconstruction stripe, with initial physisorption leading to disulfide dissociation, adatom/vacancy-pair formation, and then, at a coverage of 7.8% sulfur atoms per gold atom, surface reconstruction lifting. At higher coverages, monolayer formation proceeds similarly on the unreconstructed surface, leading to surface pitting. Formation of the analogous adatom/vacancy-pair bound dissociated adsorbate complex on exposure of the clean unreconstructed surface to methanethiol is shown to be endothermic, however.

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     School of Chemistry, The University of Sydney.

     School of Molecular and Microbial Biosciences, The University of Sydney.

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    In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

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