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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
Copyright © 2007 American Chemical Society

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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.


    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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