Nondissociative Chemisorption of Short Chain Alkanethiols on Au(111)

Rzeznicka, Izabela Irena; Lee, Junseok; Maksymovych, Peter; Yates, John T.

doi:10.1021/jp058124r

Cited by 90 publications

(137 citation statements)

References 31 publications

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“…In the 2 3 p phase, the Au-thiolate complex occupies both fcc and hcp sites, the energy of these local sites is essentially identical, and the barrier for movement between them is small; intermolecular interactions then can then play a far greater role in the self-organization. The fact that the formation of Authiolate surface complexes accompanies the Au/thiol surface reaction must also influence the reaction dynamics, and is clearly consistent with the recent finding that the deprotonation reaction occurs at defects sites on the surface [28]. Finally, our observation of the same behavior in a completely different complex phase of tertiarybutlythiolate on Au(111) (for which steric hindrance precludes the formation of the 3 p phase), suggests the adatom-thiolate moiety may also occur in the far wider class of (functionalized) thiolate SAMs on Au(111).…”

Section: Fig 1 (Color Online) Side View Of Ausupporting

confidence: 88%

True Nature of an Archetypal Self-Assembly System: Mobile Au-Thiolate Species on Au(111)

et al. 2006

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Alkanethiol self-assembled monolayer (SAM) phases on Au(111) have been assumed to involve direct S head group bonding to the substrate. Using x-ray standing wave experiments, we show the thiolate actually bonds to gold adatoms; self-organization in these archetypal SAM systems must therefore be governed by the movement of these Au-S-R moieties on the surface between two distinct local hollow sites on the surface. The results of recent ab initio total energy calculations provide strong support for this description, and a rationale for the implied significant molecular mobility in these systems. Self-assembled monolayers (SAMs) of molecular systems have attracted huge interest over the last decade or more (e.g., [1][2][3]). The archetypal SAM system of straightchain alkanethiols [CH 3 CH 2 nÿ1 SH] chemisorbed on Au(111) is the subject of many investigations, yet the structure of the molecule-substrate interface, which strongly influences the molecular ordering, remains in doubt [4]. Here we show that a quantitative investigation of this interface structure leads us to conclude that the true nature of the self-assembly in these SAMs is not organization of adsorbed molecules on the Au(111) surface, but rather organization on the surface of Au-thiolate complexes formed by the bonding of the deprotonated thiol molecule to single Au adatoms. Our results resolve two major puzzles in these systems: (i) why do all previous total energy calculations fail to agree with experiment over the adsorption site of the simplest methylthiolate species (n 1, CH 3 S) [5,6]; (ii) why is interchange between the several ordered structures of the molecules in their standing-up orientation so facile? This modified view of the interface has major implications for our understanding of the local ordering in these SAMs, and the influence of the corrugated adsorbate-substrate potential relative to the interadsorbate forces.

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Section: Fig 1 (Color Online) Side View Of Ausupporting

confidence: 88%

True Nature of an Archetypal Self-Assembly System: Mobile Au-Thiolate Species on Au(111)

et al. 2006

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“…Thiol-based SAMs are also sensitive to heating, and their thermal stability is limited to 400 K [101]. Above this temperature, thiol molecules start to desorb in the form of disulfides, suggesting that the Au-S bond is weaker than the S-C bond of thiols [102]. Some discrepancy, however, exists about the thermal stability of monolayers of thiol [103].…”

Section: Electrode Functionalizationmentioning

confidence: 99%

Controlling Redox Enzyme Orientation at Planar Electrodes

et al. 2018

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Abstract:Redox enzymes, which catalyze reactions involving electron transfers in living organisms, are very promising components of biotechnological devices, and can be envisioned for sensing applications as well as for energy conversion. In this context, one of the most significant challenges is to achieve efficient direct electron transfer by tunneling between enzymes and conductive surfaces. Based on various examples of bioelectrochemical studies described in the recent literature, this review discusses the issue of enzyme immobilization at planar electrode interfaces. The fundamental importance of controlling enzyme orientation, how to obtain such orientation, and how it can be verified experimentally or by modeling are the three main directions explored. Since redox enzymes are sizable proteins with anisotropic properties, achieving their functional immobilization requires a specific and controlled orientation on the electrode surface. All the factors influenced by this orientation are described, ranging from electronic conductivity to efficiency of substrate supply. The specificities of the enzymatic molecule, surface properties, and dipole moment, which in turn influence the orientation, are introduced. Various ways of ensuring functional immobilization through tuning of both the enzyme and the electrode surface are then described. Finally, the review deals with analytical techniques that have enabled characterization and quantification of successful achievement of the desired orientation. The rich contributions of electrochemistry, spectroscopy (especially infrared spectroscopy), modeling, and microscopy are featured, along with their limitations.

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“…[6], [7]. Kondoh et al observed that methanethiolate occupies the atop site on the perfect Au(111) surface [17], but here our adsorbate is methanethiol.…”

mentioning

confidence: 97%

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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Nondissociative Chemisorption of Short Chain Alkanethiols on Au(111)

Cited by 90 publications

References 31 publications

True Nature of an Archetypal Self-Assembly System: Mobile Au-Thiolate Species on Au(111)

True Nature of an Archetypal Self-Assembly System: Mobile Au-Thiolate Species on Au(111)

Controlling Redox Enzyme Orientation at Planar Electrodes

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

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