Ordered Anion Adlayers on Metal Electrode Surfaces

Om, Magnussen

doi:10.1021/cr000069p

Cited by 697 publications

(885 citation statements)

References 408 publications

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“…[22][23][24][25] Besides a range of pure electrochemical methods such as voltammetry, chronocoulometry and impedance spectroscopy, a number of surface sensitive techniques have been combined with electrochemistry and developed into overall in situ techniques. Research on organic molecular adsorption on single-crystal electrode surfaces has been most fruitful.…”

Section: Qijin Chimentioning

confidence: 99%

“…78,79 In such configuration, both the STM substrate and tip are fully controlled by the electrochemical potential versus a common reference electrode. Using in situ STM, reconstruction of metallic electrode surfaces at the solid/liquid interfaces under electrochemical potential control, 80 metal deposition, [81][82][83] anion adsorption 25,84,85 and organic molecule adsorption 82 have been characterized at atomic or/and molecular level. In situ STM has even been employed for nanofabrication of metallic nanoclusters or pits with precise positioning and designed patterns on the well defined surfaces.…”

Section: In Situ Scanning Tunnelling Microscopymentioning

confidence: 99%

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Electrochemically controlled self-assembled monolayers characterized with molecular and sub-molecular resolution

Zhang

Welinder

Chi

et al. 2011

Phys. Chem. Chem. Phys.

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Self-assembled organization of functional molecules on solid surfaces has developed into a powerful and sophisticated tool for surface chemistry and nanotechnology. A number of reviews on the topic have been available since the mid 1990s. This perspective article aims to focus on recent development in the investigations of electronic structures and assembling dynamics of electrochemically controlled self-assembled monolayers (SAMs) of thiol containing molecules on gold surfaces. A brief introduction is first given and particularly illustrated by a Table summarizing the molecules studied, the surface lattice structures and the experimental operating conditions. This is followed by discussion of two major high-resolution experimental methods, scanning tunnelling microscopy (STM) and single-crystal electrochemistry. In Section 3, we briefly address choice of supporting electrolytes and substrate surfaces, and their effects on the SAM structures. Section 4 constitutes the major body of the article by offering some details of recent studies for the selected cases, including in situ monitoring of assembling dynamics, molecular electronic structures, and the key external factors determining the SAM packing. In Section 5, we give examples of what can be offered by theoretical computations for the detailed understanding of the SAM electronic structures revealed by STM images. A brief summary of the current applications of SAMs in wiring metalloproteins, design and fabrication of sensors, and single-molecule electronics is described in Section 6. In the final two sections (7 and 8), we discuss the current status in understanding of electronic structures and properties of SAMs in electrochemical environments and what could be expected for future perspectives.

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Section: Qijin Chimentioning

confidence: 99%

Section: In Situ Scanning Tunnelling Microscopymentioning

confidence: 99%

Electrochemically controlled self-assembled monolayers characterized with molecular and sub-molecular resolution

Zhang

Welinder

Chi

et al. 2011

Phys. Chem. Chem. Phys.

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“…The structures with the highest reaching probability are those in the middle of the plot; however, no particular structure is favored in striking difference with cells of = 1 3 . Another interesting comparison can be made for the C 25 75 and C 25 73 cells, whose density of minima is shown in Fig. 4.…”

Section: Resultsmentioning

confidence: 99%

Comprehensive study of the potential energy surface minima of a monolayer on (111) surface

Tkatchenko

2007

Phys. Rev. B

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The potential energy landscape of a monolayer adsorbed on well-ordered ͑111͒ surface is analyzed for periodic cells with a variable number of adsorbate ͑N ads ͒ and substrate ͑N sub ͒ particles. The atom-surface potential is described by the first Fourier series term with variable corrugation, while the lateral interaction in the monolayer is modeled by a repulsive exponential term. Special attention is devoted to the determination of the total number of minima for given N ads and N sub and the probability of relaxation to the global minimum in each of the unit cells, as well as the construction of the lowest energy versus coverage curve as a function of the atom-surface potential corrugation. We find that the global appearance of the energy landscape in the majority of the unit cells is particularly simple, characterized by the global minimum positioned in a very wide basin and the high-energy minima forming a tail structure. However, this rule is broken for several unit cells when the corrugation of the atom-surface potential becomes large, making the location of the global minimum a rather difficult task. Despite the simplicity of our model, phase transitions from commensurate to striped incommensurate to hexagonal incommensurate rotated structures are observed.

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“…In particular, the progress becomes obvious after use of electrodes with well-defined surfaces, electron spectroscopies such as low energy electron diffraction (LEED) and Auger, 1,[4][5][6] and new techniques for characterization and visualization of the adsorbed layers with atomic resolution, such as scanning tunneling microscopy (STM), atomic force microscopy (AFM), and surface X-ray structure (SXS). 3 As a result, nowadays, we have a clear idea and evidence of different types of halide structures on metal surfaces such as Au(111), Ag(111), and Pt(111). Indeed, our interest and knowledge is expanded further than just adlayer structure characterization, to thermodynamics, anion-metal interactions, and other physical and chemical properties.…”

Section: Introductionmentioning

confidence: 99%

Unequal-Sphere Packing Model for Simulation of the Uniaxially Compressed Iodine Adlayer on Au(111)

Tkatchenko

Batina

2005

J. Phys. Chem. B

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A simple unequal-sphere packing (USP) model, based on pure geometrical principles, was applied to study the centered-rectangular iodine c(p× 3)R30°adlayer on the Au(111) surface, well-known from surface X-ray structure (SXS), low energy electron diffraction (LEED), and scanning tunneling microscopy (STM) experiments. To reproduce the exact patterns observed in experiments, two selective conditionssminimum average adsorbate height and minimum adlayer roughnessswere imposed. As a result, a series of adlayer patterns with c(p× 3)R30°symmetry (2.3 < p < 3), with precise structural details, including atomic registry and identification of the p-bisector as the most likely trajectory for the iodine adatom movement during the so-called uniaxial compression phenomenon, were identified. In addition, using the same model, the difference between the iodine adlayer arranged in hexagonal and centered-rectangular c(p× 3)R30°patterns, as in the case of Pt (111) and Au(111) surfaces, was investigated. Qualitative and quantitative comparison shows that iodine adatoms in these two arrangements differ significantly in atomic registry, distance from the substrate, and the adlayer corrugation. Our findings could be of special interest in the study of the nature of the iodine adatom bonding to different substrates (i.e., Au vs Pt).

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Ordered Anion Adlayers on Metal Electrode Surfaces

Cited by 697 publications

References 408 publications

Electrochemically controlled self-assembled monolayers characterized with molecular and sub-molecular resolution

Electrochemically controlled self-assembled monolayers characterized with molecular and sub-molecular resolution

Comprehensive study of the potential energy surface minima of a monolayer on (111) surface

Unequal-Sphere Packing Model for Simulation of the Uniaxially Compressed Iodine Adlayer on Au(111)

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