Scanning Tunneling Microscopy Investigation of Sulfide and Alkanethiolate Adlayers on Ag(111)

Heinz, R.; Rabe, Jürgen P.

doi:10.1021/la00002a024

Cited by 96 publications

(136 citation statements)

References 5 publications

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“…Initial STM studies of the methylthiolate adsorption phase showed, under different tip conditions, either the 7 periodicity of the true commensurate surface mesh or the (7/3) periodicity implied for the thiolate sub-mesh [31], while more recently we have reported images that show both periodicities simultaneously [32]; all observed atomic protrusions are on a (7/3) mesh, but one third of these, on a regular 7 mesh, are slightly higher above the surface than the others. These observations seem to confirm the idea that the thiolate species do lie on the expected submesh, but still provide no detailed information on the interface structure.…”

Section: Ag(111)mentioning

confidence: 99%

The interface structure of n-alkylthiolate self-assembled monolayers on coinage metal surfaces

Woodruff

2008

Phys. Chem. Chem. Phys.

124

150

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The current state of understanding of the structure of the metal/thiolate interface of nalkylthiolate 'self-assembled monolayers' (SAMs) on Cu(111), Ag(111) and Au (111) is reviewed. On Cu(111) and Ag (111) there is now clear evidence that adsorbate-induced reconstruction of the outermost metal layer occurs to a less atomically-dense structure, with the S head-group atom bonded to four-fold and three-fold coordinated hollow sites, respectively, and that intermolecular interaction plays some role in the periodicity of the resulting SAMs. On the far more heavily-studied Au(111) surface, the detailed interface structure remains controversial, but there is growing evidence for the role of Au-adatomthiolate moieties in the layer ordering.

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Section: Ag(111)mentioning

confidence: 99%

The interface structure of n-alkylthiolate self-assembled monolayers on coinage metal surfaces

Woodruff

2008

Phys. Chem. Chem. Phys.

124

150

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“…• structure [36,37]. Normal incident X-ray standing wave (NIXSW) experiments have confirmed the √ 7 × √ 7 structure, but have corrected the registry of the SAM on the underlying substrate to (…”

Section: Structuresmentioning

confidence: 99%

Dipole Formation at Interfaces of Alkanethiolate Self-assembled Monolayers and Ag(111)

2007

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The formation of interface dipoles in self-assembled monolayers (SAMs) of -CH3 and -CF3 terminated short-chain alkanethiolates on Ag(111) is studied by means of density functional theory calculations. The interface dipoles are characterized by monitoring the change in the surface work function upon adsorption of the SAM. We compare results obtained for SAMs in structures with a different packing density of molecules, i.e. (• , and p(2×2). The work function of alkanethiolate SAMs on silver depends weakly on the packing density; that of fluorinated alkanethiolates shows a stronger dependance. The results are analyzed in terms of two nearly independent contributions to the interface dipole. These originate respectively from the molecular dipoles and from a charge transfer between the metal surface and the molecules. The charge transfer is determined by the silver-sulfur bond and it is independent of the electronegativity of the molecules.

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“…Concerning the specific interaction of H 2 S with Ag͑111͒, almost all previous studies have focused on using H 2 S as a source of adsorbed S. In those studies, dissociative adsorption was achieved using high pressure and/or elevated surface temperature when H 2 S was in the gas phase, [1][2][3][4][5][6][7] or using electrochemical methods when H 2 S was in liquid solution. 7,8 In contrast, the present paper deals with the state of the molecule that is obtained by adsorption at low pressure and at temperatures ͑T͒ of 5-30 K.…”

Section: Introductionmentioning

confidence: 99%

Low-temperature adsorption of H2S on Ag(111)

Russell

Liu

Kawai

et al. 2010

The Journal of Chemical Physics

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H 2 S forms a rich variety of structures on Ag(111) at low temperature and submonolayer coverage. The molecules decorate step edges, exist as isolated entities on terraces, and aggregate into clusters and islands, under various conditions. One type of island exhibits a (×)R25.3° unit cell. Typically, molecules in the clusters and islands are separated by about 0.4 nm, the same as the S-S separation in crystalline H 2 S. Density functional theory indicates that hydrogen-bonded clusters contain two types of molecules. One is very similar to an isolated adsorbed H 2 S molecule, with both S-H bonds nearly parallel to the surface. The other has a S-H bond pointed toward the surface. The potential energy surface for adsorption and diffusion is very smooth. KeywordsAmes Laboratory, adsorption, density functional theory, diffusion, hydrogen bonds, intermolecular forces, island structure, molecular clusters, potential energy surfaces, silver, sulphur compounds H 2 S forms a rich variety of structures on Ag͑111͒ at low temperature and submonolayer coverage. The molecules decorate step edges, exist as isolated entities on terraces, and aggregate into clusters and islands, under various conditions. One type of island exhibits a ͑ ͱ 37ϫ ͱ 37͒R25.3°unit cell.Typically, molecules in the clusters and islands are separated by about 0.4 nm, the same as the S-S separation in crystalline H 2 S. Density functional theory indicates that hydrogen-bonded clusters contain two types of molecules. One is very similar to an isolated adsorbed H 2 S molecule, with both S-H bonds nearly parallel to the surface. The other has a S-H bond pointed toward the surface. The potential energy surface for adsorption and diffusion is very smooth.

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Scanning Tunneling Microscopy Investigation of Sulfide and Alkanethiolate Adlayers on Ag(111)

Cited by 96 publications

References 5 publications

The interface structure of n-alkylthiolate self-assembled monolayers on coinage metal surfaces

The interface structure of n-alkylthiolate self-assembled monolayers on coinage metal surfaces

Dipole Formation at Interfaces of Alkanethiolate Self-assembled Monolayers and Ag(111)

Low-temperature adsorption of H2S on Ag(111)

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