Effect of the atomic configuration of gold electrodes on the electrical conduction of alkanedithiol molecules

Müller, K.‐H.

doi:10.1103/physrevb.73.045403

Cited by 135 publications

(107 citation statements)

References 39 publications

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“…This uses the SIESTA method to obtain the electronic structure and calculates transport by using the non-equilibrium Green's function method. This code has now been used extensively in the literature, for example, other studies have been undertaken to investigate the effect of different bonding geometries of small organic molecules between gold electrodes on the current-voltage characteristics of the system [27][28][29].…”

Section: Methodsmentioning

confidence: 99%

The effect of reciprocal-space sampling and basis set quality on the calculated conductance of a molecular junction

Hoft

Ford

Cortie

2007

Molecular Simulation

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We perform density functional theory and non-equilibrium Green's Function calculations of the conductance of a gold wire and a 1,4-phenylenedimethanethiol (XYL) molecule adsorbed between Au(111) electrodes using the TranSIESTA software package.The effect of varying different computational parameters is investigated. We find that the conductance is more sensitive to the reciprocal space sampling grid than the quality of the basis set employed. The conductance can vary up to a factor of five as a result of the choice of computational parameters. We report a set of computational parameters that yields a well-converged conductance value.

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Section: Methodsmentioning

confidence: 99%

The effect of reciprocal-space sampling and basis set quality on the calculated conductance of a molecular junction

Hoft

Ford

Cortie

2007

Molecular Simulation

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“…Indeed, in the limit of very small clusters, the binding must reduce to the Au(I)-thiolate structures that are well established for small molecular species. Of interest in this regard too are scanning tunnelling microscopy (STM) break-junction experiments in which STM tips are run into SAMs and then withdrawn, pulling out monatomic gold wires that eventually break (73). This constitutes the reverse process to nanoparticle growth, taking stable Au(0)-thiyl interfaces and converting them to Au(I)-thiolates in solution.…”

Section: Application To Molecules and Monolayers Containing Au-s Bondsmentioning

confidence: 99%

Gold surfaces and nanoparticles are protected by Au(0)–thiyl species and are destroyed when Au(I)–thiolates form

Reimers

Ford

Halder

et al. 2016

Proc. Natl. Acad. Sci. U.S.A.

126

163

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The synthetic chemistry and spectroscopy of sulfur-protected gold surfaces and nanoparticles is analyzed, indicating that the electronic structure of the interface is Au(0)-thiyl, with Au(I)-thiolates identified as high-energy excited surface states. Density-functional theory indicates that it is the noble character of gold and nanoparticle surfaces that destabilizes Au(I)-thiolates. Bonding results from large van der Waals forces, influenced by covalent bonding induced through s-d hybridization and charge polarization effects that perturbatively mix in some Au(I)-thiolate character. A simple method for quantifying these contributions is presented, revealing that a driving force for nanoparticle growth is nobleization, minimizing Au(I)-thiolate involvement. Predictions that Brust-Schiffrin reactions involve thiolate anion intermediates are verified spectroscopically, establishing a key feature needed to understand nanoparticle growth. Mixing of preprepared Au(I) and thiolate reactants always produces Au(I)-thiolate thin films or compounds rather than monolayers. Smooth links to O, Se, Te, C, and N linker chemistry are established.gold-sulfur bonding | synthesis | mechanism | electronic structure | nanoparticle G old self-assembled monolayers (SAMs) and monolayerprotected gold nanoparticles form important classes of systems relevant for modern nanotechnological and sensing applications (1-5). Understanding the chemical nature of these interfaces is critical to the design of new synthesis techniques, the design of new spectroscopic methods to investigate them, and to developing system properties or device applications. Over the last 10 y, great progress has been made in understanding the atomic structures of gold-sulfur interfaces (6). Most discussion (7) has focused on the identification of adatom-bound motifs of the form RS-Au-SR (where R is typically a linear alkyl chain or phenyl group) sitting above a regular Au(111) surface (8-10) or on top of a nanoparticle core of regular geometry (11), Other variant structures have also been either observed, such as polymeric chains such as the trimer RS-Au-SR-Au-SR) (10, 11), or proposed (8,12,13). By considering the four isomers of butanethiol (14), we have shown that alternative structures can also be produced in which RS groups bind directly to an Au(111) surface without gold adatoms. This occurs whenever steric interactions across the adatoms are too strong or steric intermolecular packing forces allow for very high surface coverages if both adatom and directly bound motifs coexist in the same regular SAM (15). The cross-adatom steric effect has also been demonstrated for gold nanoparticles (16), and we have shown that Coulombic interactions between charged tail groups can also inhibit adatom formation (17). SAMs involving adatoms have poor longrange order owing to the surface pitting that is required to deliver gold adatoms, while directly bound motifs lead to regular surfaces (18).There is clearly a delicate balance between the forces that direct these different in...

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“…The thiol (−SH) group is the most commonly used anchoring group, especially when the electrodes are made of gold, because of their high covalent bond strength. 28 However, the thiol group has been shown to lead to a large variety of binding geometries, [29][30][31] which implies a large spread in the observed conductance values. Many different alternatives to the thiol group have been explored in recent years.…”

Section: Introductionmentioning

confidence: 99%

Theoretical study of the charge transport through C60-based single-molecule junctions

et al. 2012

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We present a theoretical study of the conductance and thermopower of single-molecule junctions based on C 60 and C 60 -terminated molecules. We first analyze the transport properties of gold-C 60 -gold junctions and show that these junctions can be highly conductive (with conductances above 0.1G 0 , where G 0 = 2e 2 /h is the quantum of conductance). Moreover, we find that the thermopower in these junctions is negative due to the fact that the lowest unoccupied molecular orbital dominates the charge transport, and its magnitude can reach several tens of microvolts per kelvin, depending on the contact geometry. On the other hand, we study the suitability of C 60 as an anchoring group in single-molecule junctions. For this purpose, we analyze the transport through several dumbbell derivatives using C 60 as anchors, and we compare the results with those obtained with thiol and amine groups. Our results show that the conductance of C 60 -terminated molecules is rather sensitive to the binding geometry. Moreover, the conductance of the molecules is typically reduced by the presence of the C 60 anchors, which in turn makes the junctions more sensitive to the functionalization of the molecular core with appropriate side groups.

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Effect of the atomic configuration of gold electrodes on the electrical conduction of alkanedithiol molecules

Cited by 135 publications

References 39 publications

The effect of reciprocal-space sampling and basis set quality on the calculated conductance of a molecular junction

The effect of reciprocal-space sampling and basis set quality on the calculated conductance of a molecular junction

Gold surfaces and nanoparticles are protected by Au(0)–thiyl species and are destroyed when Au(I)–thiolates form

Theoretical study of the charge transport through C60-based single-molecule junctions

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