Direct observation of sulfur dimers in alkanethiol self-assembled monolayers on Au(111)

Kluth, G. Jonathan; Carraro, Carlo; Maboudian, Roya

doi:10.1103/physrevb.59.r10449

Cited by 120 publications

(137 citation statements)

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“…Our calculation indicates that two intact methanethiol molecules do not form a dimer on the perfect Au(111) surface, which is consistent with the respective observation in Refs. [17], [24] and [25]. These findings resolve the controversial issue of bond cleavage at low or room temperature.…”

supporting

confidence: 54%

“…The emergence of thiolate on the Au(111) surface reflects the presence of surface defects. Defects might be caused in the process of gold surface production, or temperature enhancement [24] or exposure to X-rays [27]. The sulfur dimers were proposed on the basis of X-ray diffraction (XRD) data obtained at saturated coverage [28], but we have found that a pair of intact methanethiols cannot form a dimer on the defectfree Au(111) surface.…”

mentioning

confidence: 99%

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Do Methanethiol Adsorbates on the Au(111) Surface Dissociate?

Zhou

Hagelberg

2006

Phys. Rev. Lett.

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The interaction of methanethiol molecules CH3SH with the Au(111) surface is investigated, and it is found for the first time that the S-H bond remains intact when the methanethiol molecules are adsorbed on the regular Au(111) surface. However, it breaks if defects are present in the Au(111) surface. At low coverage, the fcc region is favored for S atom adsorption, but at saturated coverage the adsorption energies at various sites are almost iso-energetic. The presented calculations show that a methanethiol layer on the regular Au(111) surface does not dimerize.

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supporting

confidence: 54%

mentioning

confidence: 99%

Do Methanethiol Adsorbates on the Au(111) Surface Dissociate?

Zhou

Hagelberg

2006

Phys. Rev. Lett.

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“…The major peak positions are in good agreement with those reported previously for incubated octadecanethiol/Au(111). 29 In contrast to the IRRAS spectra for 1,6 HDT, several modes are observed in the 1000-1500 cm -1 region and can be assigned to CH 2 bending modes and C-C stretch modes. The mode at 720 cm -1 can be assigned to the C-S stretch.…”

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confidence: 82%

Electrochemically Driven Assembly of Mixed Dithiol Bilayers via Sulfur Dimers

et al. 2003

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Vous avez des questions? Nous pouvons vous aider. Pour communiquer directement avec un auteur, consultez la première page de la revue dans laquelle son article a été publié afin de trouver ses coordonnées. Si vous n'arrivez pas à les repérer, communiquez avec nous à PublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. Questions? Contact the NRC Publications Archive team atPublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. If you wish to email the authors directly, please see the first page of the publication for their contact information. NRC Publications Archive Archives des publications du CNRCThis publication could be one of several versions: author's original, accepted manuscript or the publisher's version. / La version de cette publication peut être l'une des suivantes : la version prépublication de l'auteur, la version acceptée du manuscrit ou la version de l'éditeur. For the publisher's version, please access the DOI link below./ Pour consulter la version de l'éditeur, utilisez le lien DOI ci-dessous.Access and use of this website and the material on it are subject to the Terms and Conditions set forth at NRC Publications Record / Notice d'Archives des publications de CNRC:http://nparc.cisti-icist.nrc-cnrc.gc.ca/eng/view/object/?id=2b9ba878-0bb9-4dc2-87a4-1fa06edbed60 http://nparc.cisti-icist.nrc-cnrc.gc.ca/fra/voir/objet/?id=2b9ba878-0bb9-4dc2-87a4-1fa06edbed60 We report on the electroformation of mixed bilayers of rigid (1,4-benzenedimethanethiol) and flexible (1,6-hexanedithiol) dithiols on Au(111) from alkaline aqueous solution. These bilayers are formed by first electrodepositing a monolayer of vertically aligned dithiols. The unreacted dithiols are then oxidatively dimerized with the other dithiols, and a bilayer is formed. ACIS (ac impedance spectroscopy) measurements indicate that the monolayer of the rigid dithiol is a better substrate for dimerization than the flexible dithiol. ACIS also reveals that the electroformation of a bilayer is more complete, and the bilayer has fewer defects than one obtained through chemical incubation. Infrared reflection-absorption spectroscopy provides proof for mixed-bilayer formation of the alkanedithiol with the benzenedimethanethiol having its methylene groups deuterated. The mechanism for bilayer formation via the oxidative dimerization of thiols is supported by high-resolution electron energy loss spectra of bilayers, which show a S-S stretch at 515 cm -1 . Our results show that this electrochemical approach is a viable methodology for the formation of complex organic interfaces.

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“…From infrared data it was concluded that there are two different orientations in the alkyl chains [40] and from grazing incidence X-ray diffraction data, a model was proposed for the superstructure based upon thiolate dimers [41]. Evidence against the dimer model was presented by scanning tunneling microscopy [42] and by electron spectroscopy experiments [43]; in the latter, thiolate dimers were found only at temperatures above 375K. In recent He and X-ray diffraction experiments it was concluded that in the (4 2) c × superstructure alkyl-thiolate molecules adsorb as monomers on the Au(111) surface [44,45].…”

Section: Structuresmentioning

confidence: 99%

Surface Dipoles and Work Functions of Alkylthiolates and Fluorinated Alkylthiolates on Au(111)

2006

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We study the dipole formation at the surface formed by -CH 3 and -CF 3 terminated shortchain alkyl-thiolate monolayers on Au(111). In particular, we monitor the change in work function upon chemisorption using density functional theory calculations. We separate the surface dipole into two contributions, resulting from the gold-adsorbate interaction and the intrinsic dipole of the adsorbate layer, respectively. The two contributions turn out to be approximately additive. Adsorbate dipoles are defined by calculating dipole densities of free-standing molecular monolayers. The gold-adsorbate interaction is to a good degree determined by the Au-S bond only. This bond is nearly apolar and its contribution to the surface dipole is relatively small. The surface dipole of the self-assembled 2 monolayer is then dominated by the intrinsic dipole of the thiolate molecules. Alkyl-thiolates increase the work function of Au(111), whereas fluorinated alkyl-thiolates decrease it.

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Direct observation of sulfur dimers in alkanethiol self-assembled monolayers on Au(111)

Cited by 120 publications

References 28 publications

Do Methanethiol Adsorbates on the Au(111) Surface Dissociate?

Do Methanethiol Adsorbates on the Au(111) Surface Dissociate?

Electrochemically Driven Assembly of Mixed Dithiol Bilayers via Sulfur Dimers

Surface Dipoles and Work Functions of Alkylthiolates and Fluorinated Alkylthiolates on Au(111)

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