Headgroup dimerization in methanethiol monolayers on the Au(111) surface: A density functional theory study

Zhou, Jian‐Ge; Williams, Quinton L.; Hagelberg, Frank

doi:10.1103/physrevb.76.075408

Cited by 15 publications

(20 citation statements)

References 36 publications

(55 reference statements)

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“…The radical‐based description of the adsorption process is the one commonly involved in the theoretical description of metal/SAM interfaces; the corresponding values reported in that study range between −1.5 and −2.0 eV and are in good agreement with other values reported from DFT calculations 32. 39–42, 64, 65, 67, 68 The values of approximately −1.9 (≈44) and −2.2 eV (≈51 kcal mol −1 ) found for the bridge position in CH 3 S/Au and CF 3 S/Au, respectively, have the same order of magnitude as the SAu bond strength, which is of the order of 40–50 kcal mol −1 69. 70 The results obtained for the fcc position are systematically lower by 0.2–0.4 eV.…”

Section: Resultsmentioning

confidence: 99%

Work‐Function Modification of Au and Ag Surfaces upon Deposition of Self‐Assembled Monolayers: Influence of the Choice of the Theoretical Approach and the Thiol Decomposition Scheme

Cornil

Wood

et al. 2013

ChemPhysChem

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We have characterized theoretically the work-function modifications of the (111) surfaces of gold and silver upon deposition of self-assembled monolayers based on methanethiol and trifluoromethanethiol. A comparative analysis is made between the experimental results and those obtained from two widely used approaches based on density functional theory. The contributions to the total work-function modifications are estimated on the basis of two decomposition schemes of the thiol molecules that have been proposed in the literature. The contributions are found to differ significantly between the two approaches, as do the corresponding adsorption energies.

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Section: Resultsmentioning

confidence: 99%

Work‐Function Modification of Au and Ag Surfaces upon Deposition of Self‐Assembled Monolayers: Influence of the Choice of the Theoretical Approach and the Thiol Decomposition Scheme

Cornil

Wood

et al. 2013

ChemPhysChem

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“…[107][108][109][110][111] Only recently, further theoretical studies could partially reconcile these discrepancies by finding that, while at full coverage adsorption as individual thiolates is clearly preferable, dimerization might indeed occur at lower coverage. [112] Adding to the confusion, further experimental evidence has been advanced, which put the sulfur exclusively at the singly coordinated on-top sites of a defect-free Au(111) surface. [113,114] These persistent inconsistencies among different experiments as well as between experiment and theory eventually led to the notion of more severe reconstructions of the topmost gold layer upon SAM formation.…”

Section: Notes On the Atomistic Structure Of The Thiol/gold Interfacementioning

confidence: 99%

Modeling the Electronic Properties of π‐Conjugated Self‐Assembled Monolayers

2010

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The modification of electrode surfaces by depositing self-assembled monolayers (SAMs) provides the possibility for controlled adjustment of various key parameters in organic and molecular electronic devices. Most important among them are the work function of the electrode and the relative alignment of its Fermi level with the conducting states in the SAM itself and with those in a subsequently deposited organic semiconductor. For the efficient application of such interface modifications it is crucial to reach a proper understanding of the relation between the chemical structure of a molecule, its molecular electronic characteristics, and the properties of the SAM formed by such molecules. Over the past years, quantum-mechanical calculations have proven to be a valuable tool for reaching a fundamental understanding of the relevant structure-property relations. Here, we provide a review over the field and report on recent progress in the modeling of the interfacial electronic properties of pi-conjugated SAMs. In addition to the insight that can be gained from simple electrostatic considerations, we focus on the quantum-mechanical description of the roles played by substituents, molecular backbones, chemical anchoring groups, and the packing density of molecules on the surface. Furthermore, we explicitly address the energy-level alignment at the interface between a prototypical organic semiconductor and a SAM-covered metal electrode and describe an approach suitable for extending the metallic character of the substrate onto the monolayer.

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“…36 It was also reported that dissociation of dimethyl disulfide (CH 3 SSCH 3 ) adsorbed on the Au(111) surface can be accomplished by applying a voltage of ∼1.4 V. 37 Existence of disulfide bonds has long been a controversy for alkanethiols and dialkyl disulfides adsorbed on gold surfaces. [37][38][39][40][41][42][43][44][45] Thus, we posed the following questions: What if the application of the bias voltage induces the formation or breakage of the disulfide bonds of 1? Would this conversion between cyclic and acyclic 1,2-dithiolane anchor groups alter the electron transport through 1, serving as an additional switching mechanism for 1 and affecting the robustness of the junction?…”

Section: Introductionmentioning

confidence: 99%

Electron Transport through Cyclic Disulfide Molecular Junctions with Two Different Adsorption States at the Contact: A Density Functional Theory Study

Jang

Goddard

2008

J. Phys. Chem. C

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1,2-Dithiolane is a promising anchor group for attaching molecules to metal electrodes in molecular junction devices. This five-membered cyclic disulfide adsorbs on Au surfaces either in a cyclic fashion (with its disulfide bond intact, via molecular adsorption) or in an acyclic fashion (with its disulfide bond broken, via dissociative adsorption). Our density functional theory calculations show that the dissociative adsorption is slightly preferred, but both are stable. We also report nonequilibrium Green's function calculations showing that molecular junctions of cyclic and acyclic 1,2-dithiolanes sandwiched between two gold electrodes exhibit essentially the same insulating current-voltage characteristics at moderate bias voltages, despite the significant difference in their states of adsorption.

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Headgroup dimerization in methanethiol monolayers on the Au(111) surface: A density functional theory study

Cited by 15 publications

References 36 publications

Work‐Function Modification of Au and Ag Surfaces upon Deposition of Self‐Assembled Monolayers: Influence of the Choice of the Theoretical Approach and the Thiol Decomposition Scheme

Work‐Function Modification of Au and Ag Surfaces upon Deposition of Self‐Assembled Monolayers: Influence of the Choice of the Theoretical Approach and the Thiol Decomposition Scheme

Modeling the Electronic Properties of π‐Conjugated Self‐Assembled Monolayers

Electron Transport through Cyclic Disulfide Molecular Junctions with Two Different Adsorption States at the Contact: A Density Functional Theory Study

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