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The empirical details and theoretical assumption for 6-[1'-(6-mercapto-hexyl)-[4, 4] bipyridinium]-hexane-1-thiol iodide (6V6) wired between a gold electrode surface and tip in an in situ scanning tunneling microscopy configuration are discussed.

Atomic features of a close-packed metal surface have been observed for the first time by scanning tunneling microscopy in organic polar solvents. Evaporated gold films, exhibiting large reconstructed (111) terraces, have been imaged with a resolution far superior to previous results in aqueous environments. [ABSTRACT FROM AUTHOR]

The single molecule conductance of the E and Z isomers of 4,4'-(ethene-1,2-diyl)dibenzoic acid has been determined using two scanning tunneling microscopy (STM) methods for forming molecular break junctions [the I(s) (I = current and s is distance) method and the in situ break junction technique]. Isomerization leads to significant changes in the electrical conductance of these molecules, with the Z isomer exhibiting a higher conductance than the E isomer. Isomerization is achieved directly on the gold surface through photoirradiation, and the STM is used to determine conductance before and after irradiation; reversible switching between the two isomers could be achieved through irradiation of the surface bound species at different wavelengths. In addition, three groups of molecular conductance values [A ("low"), B ("medium"), and C ("high")] have been measured for these carboxylate-terminated molecules. The origin of these conductance groups as well as the increase of the conductance for the Z isomer have been analyzed by comparing the length of the molecules extended in the gap, derived from molecular modeling, with the experimentally observed break-off distance for both isomers.

The measurement of the electrical properties of molecules, down to the single molecule level, has become an experimental reality in recent years. A number of methods are now available for experimentally achieving this feat. The common aim of these methods is to entrap a single or small numbers of molecules between a pair of metallic contacts. This topical review focuses on describing and comparing experimental methods for entrapping and measuring the electrical properties of single molecules in metallic contact gaps. After describing the methods, reasons are tendered for apparent discrepancies in the literature between measured single molecule conductance values, with a focus on the most widely studied alkanedithiol system. Illustrative examples are then presented of the determination of the electrical properties of a range of single molecular systems, in order to highlight the progress which has been made in recent years.

A systematic experimental study of the electrical conductance of single alkanedithiol molecules (HS-(CH(2))(N)-SH) between gold contacts in air for N = 3-12 is presented. For all of these molecules, three different fundamental conductance groups (low, medium and high conductance) were observed. For long molecules (N > 7) the conductance decays exponentially with molecular length for all three conductance groups, as it has been reported previously. In contrast, for short molecules (N < 8), it is shown that the decay of conductance with molecular length gets less pronounced for decreasing length, approaching length independent conductance values for N < 5 where the voltage dependence of the tunnelling current exhibits an anomalous behaviour. Possible reasons for these findings, including the influence of the image potential on the effective mass of the tunnelling electron (hole), are discussed.

A scanning tunnelling microscope has been used to determine the conductance of single molecular wires with the configuration X-bridge-X, X-bridge-Y and Y-bridge-Y (X = thiol terminus and Y = COOH). We find that for molecular wires with mixed functional groups (X-bridge-Y) the single molecule conductance decreases with respect to the comparable symmetric molecules. These differences are confirmed by theoretical computations based on a combination of density functional theory and the non-equilibrium Green's functions formalism. This study demonstrates that the apparent contact resistance, as well as being highly sensitive to the type of the anchoring group, is also strongly influenced by contact-asymmetry of the single molecular junction which in this case decreases the transmission. This highlights that contact-asymmetry is a significant factor to be considered when evaluating nanoelectrical junctions incorporating single molecules.

It is now becoming clear that the characteristics of the whole junction are important in determining the conductance of single molecules bound between two metal contacts. This paper shows through measurements on a series of seven conjugated molecular bridges that contact separation is an important factor in determining the electrical response of the molecular junction. These data are obtained using the I(t) method developed by Haiss et al since the scanning tunnelling microscope tip to substrate separation can be controlled through choice of the set-point (I(0)) current and calibrated with current-distance curves and knowledge of the terminal to terminal length of the molecular wire. The contact gap separation dependence is interpreted as arising from tilting of these molecules in the junction and this model is underpinned by ab initio transport computations. In this respect we make the general observation that conductance increases rather dramatically at higher tilt angle away from the normal for conformationally rigid molecular wires and that this increase in conductance arises from increased electronic coupling between the molecular bridge and the gold contacts.

We demonstrate that the electrical "switching" behavior of single molecules connected between two electrode contacts can be controlled by altering their structure and electrochemical characteristics. The electrical properties of gold|molecule|gold single molecule junctions incorporating HS(CH2)6-X-(CH2)6SH, where X = viologen (4,4'-bipyridinium) or pyrrolotetrathiafulvalene, are determined using a scanning tunneling microscopy based technique. The switching behavior, controlled through a tuneable electrochemical gate, changes from an on-off response (viologen) to an off-on-off response (pyrrolotetrathiafulvalene) on changing the central redox group. In contrast, the electrical properties of junctions incorporating redox-inactive HS(CH2)6-1,4-C6H4-(CH2)6SH do not alter significantly as a function of applied potential.

A series of thioacetate-terminated butadiyne-linked porphyrin oligomers have been synthesized with one to three porphyrin repeat units. Single molecule electrical scanning tunneling microscopy measurements using the I(s) and I(t) methods were used to determine the molecule conductances for this series of oligomers. The molecular conductance shows an exponential falloff with sulfur-sulfur distance with a remarkably low attenuation factor of beta = (0.04 +/- 0.006) A-1.

Single molecule conductance measurements on 1,4-bis-(6-thia-hexyl)-benzene derivatives reveal (i) that benzene rings serve as an effective indentation in the tunnelling barrier, and (ii) that more electron-rich benzene rings give higher conductances, consistent with hole conduction (i.e.via the benzene HOMO).

The dependence of the optical properties of spherical gold nanoparticles on particle size and wavelength were analyzed theoretically using multipole scattering theory, where the complex refractive index of gold was corrected for the effect of a reduced mean free path of the conduction electrons in small particles. To compare these theoretical results to experimental data, gold nanoparticles in the size range of 5 to 100 nm were synthesized and characterized with TEM and UV-vis. Excellent agreement was found between theory and experiment. It is shown that the data produced here can be used to determine both size and concentration of gold nanoparticles directly from UV-vis spectra. Equations for this purpose are derived, and the precision of various methods is discussed. The major aim of this work is to provide a simple and fast method to determine size and concentration of nanoparticles.

There is much discussion of molecules as components for future electronic devices. However, the contacts, the local environment and the temperature can all affect their electrical properties. This sensitivity, particularly at the single-molecule level, may limit the use of molecules as active electrical components, and therefore it is important to design and evaluate molecular junctions with a robust and stable electrical response over a wide range of junction configurations and temperatures. Here we report an approach to monitor the electrical properties of single-molecule junctions, which involves precise control of the contact spacing and tilt angle of the molecule. Comparison with ab initio transport calculations shows that the tilt-angle dependence of the electrical conductance is a sensitive spectroscopic probe, providing information about the position of the Fermi energy. It is also shown that the electrical properties of flexible molecules are dependent on temperature, whereas those of molecules designed for their rigidity are not.

We report here on the fabrication of a three-dimensional array of nanoparticles which bridges the gap between lithographically defined gold electrode contacts separated by 20 nm. The nanoparticle assemblies are formed from about 5 nm gold nanoparticles and benzenedimethanethiol (BDMT) bridging ligands. These assemblies are introduced between the contacts using a layer-by-layer protocol with successive BDMT self-assembly being followed by nanoparticle adsorption until the gap is bridged. The temperature dependent electrical properties of these devices are analysed to establish whether they are consistent with the notion that the networks are built up from molecularly interlinked discrete gold nanoparticles. To aid this analysis the molecular conductance of single bridging molecules is also characterized at room temperature using a recently introduced method based on the scanning tunnelling microscope (STM). From these measurements it is concluded that the room temperature electrical properties of the nanostructured networks are limited by the small interparticle connectivity and the inherent resistance of the linker molecules.

The temperature dependence of the single molecule conductance (SMC) of alpha,omega-alkanedithiols has been investigated using a scanning tunnelling microscopy (STM) method. This is based on trapping molecules between a gold STM tip and a gold substrate and measuring directly the current across the molecule under different applied potentials. A pronounced temperature dependence of the conductance, which scales logarithmically with T(1), is observed in the temperature range between 293 and 353 K. It is proposed the origin of this dependence is the change in distribution between molecular conformers rather than changes in either the conduction mechanism or the electronic structure of molecule. For alkanedithiols the time averaged conformer distribution shifts to less elongated conformers at higher temperatures thus giving rise to higher conductance across the molecular bridges. This is analysed by first calculating energy differences between different conformers and then calculating their partition distribution. A simple tunnelling model is then used to calculate the temperature dependent conductance based on the conformer distribution. These findings demonstrate that charge transport through single organic molecules at ambient temperatures is a subtle and highly dynamic process that cannot be described by analysing only one molecular conformation corresponding to the lowest energy geometry of the molecule.

Gold nanoparticles were used to make electrical contact to redox-active organic molecules. Viologen based dithiols were self-assembled from solution on Au(111) for use as tethers to attach nanoparticles to a conducting substrate. The topography and electrical properties of the resulting films were investigated by STM and STS and the orientation of these linkers was investigated by FTIR. Surface coverage increased with increasing reaction time, resulting in a change of film orientation from a flat to a more upright standing conformation. Gold nanoparticles attached to these self-assembled films were characterised by STM. It was possible to isolate a single redox-active molecule in an alkanethiol matrix and by subsequent attachment of a single gold nanoparticle the electrical properties of single wired molecules could be investigated. This method allowed the measurement of the conductivity of single molecules connecting a nanoparticle to the substrate chemically, thus forming stable electrical contacts at both ends.

Spontaneous formation of stable molecular wires between a gold scanning tunneling microscopy (STM) tip and substrate is observed when the sample has a low coverage of alpha,omega-dithiol molecules and the tunneling resistance is made sufficiently small. Current-distance curves taken under these conditions exhibit characteristic current plateaux at large tip-substrate separations from which the conductivity of a single molecule can be obtained. The versatility of this technique is demonstrated using redox-active molecules under potential control, where substantial reversible conductivity changes from 0.5 to 2.8 nS were observed when the molecule was electrochemically switched from the oxidized to the reduced state.

In situ FTIR spectroscopy has been used in the attenuated total reflectance (ATR) mode to investigate the surface chemistry of etching Si(100) surfaces in aqueous KOH. The effect of solution concentration and electrode potential on the Si-H vibrations has been explored and the experimental results compared with density functional theory calculations. In addition. the kinetics of surface passivation of n-Si(100) has been investigated using FTIR spectroscopy.