Oxygen enhanced atomic chain formation

We report experimental evidence for atomic chain formation during stretching of atomic-sized contacts for gold and silver, that is strongly enhanced due to oxygen incorporation. While gold has been known for its tendency to form atomic chains, for silver this is only observed in the presence of oxygen. With oxygen the silver chains are as long as those for gold, but the conductance drops with chain length to about 0.1 conductance quantum. A relation is suggested with previous work on surface reconstructions for silver (110) surfaces after chemisorption of oxygen.Comment: 4 pages, 4 figure

Vibrationally Induced Two-Level Systems in Single-Molecule Junctions

Single-molecule junctions are found to show anomalous spikes in dI/dV spectra. The position in energy of the spikes are related to local vibration mode energies. A model of vibrationally induced two-level systems reproduces the data very well. This mechanism is expected to be quite general for single-molecule junctions. It acts as an intrinsic amplification mechanism for local vibration mode features and may be exploited as a new spectroscopic tool.Comment: 4 pages, 4 figure

Electrostatic potential between charged particles at an oil-water interface

Electrostatic interactions between point charges embedded into interfaces separating dielectric media are omnipresent in soft matter systems and often control their stability. Such interactions are typically complicated and do not resemble their bulk counterparts. For instance, the electrostatic potential of a point charge at an air-water interface falls off as $r^{-3}$, where $r$ is the distance from the charge, exhibiting a dipolar behaviour. This behaviour is often assumed to be generic, and is widely referred to when interpreting experimental results. Here we explicitly calculate the in-plane potential of a point charge at an interface between two electrolyte solutions with different dielectric permittivities and Debye screening lengths. We show that the asymptotic behaviour of this potential is neither a dipole, which characterises the potential at air-water interfaces, nor a screened monopole, which describes the bulk behaviour in a single electrolyte solution. By considering the same problem in arbitrary dimensions, we find that the physics behind this difference can be traced to the asymmetric propagation of the interaction in the two media. Our results are relevant, for instance, to understand the physics of charged colloidal particles trapped at oil-water interfaces.Comment: 11 pages, 7 figure

Emulsification in binary liquids containing colloidal particles: a structure-factor analysis

We present a quantitative confocal-microscopy study of the transient and final microstructure of particle-stabilised emulsions formed via demixing in a binary liquid. To this end, we have developed an image-analysis method that relies on structure factors obtained from discrete Fourier transforms of individual frames in confocal image sequences. Radially averaging the squared modulus of these Fourier transforms before peak fitting allows extraction of dominant length scales over the entire temperature range of the quench. Our procedure even yields information just after droplet nucleation, when the (fluorescence) contrast between the two separating phases is scarcely discernable in the images. We find that our emulsions are stabilised on experimental time scales by interfacial particles and that they are likely to have bimodal droplet-size distributions. We attribute the latter to coalescence together with creaming being the main coarsening mechanism during the late stages of emulsification and we support this claim with (direct) confocal-microscopy observations. In addition, our results imply that the observed droplets emerge from particle-promoted nucleation, possibly followed by a free-growth regime. Finally, we argue that creaming strongly affects droplet growth during the early stages of emulsification. Future investigations could clarify the link between quench conditions and resulting microstructure, paving the way for tailor-made particle-stabilised emulsions from binary liquids.Comment: http://iopscience.iop.org/0953-8984/22/45/455102

Image effects in transport at metal-molecule interfaces

We present a method for incorporating image-charge effects into the description of charge transport through molecular devices. A simple model allows us to calculate the adjustment of the transport levels, due to the polarization of the electrodes as charge is added to and removed from the molecule. For this, we use the charge distributions of the molecule between two metal electrodes in several charge states, rather than in gas phase, as obtained from a density-functional theory-based transport code. This enables us to efficiently model level shifts and gap renormalization caused by image-charge effects, which are essential for understanding molecular transport experiments. We apply the method to benzene di-amine molecules and compare our results with the standard approach based on gas phase charges. Finally, we give a detailed account of the application of our approach to porphyrin-derivative devices recently studied experimentally by Perrin et al. [Nat. Nanotechnol. 8, 282 (2013)], which demonstrates the importance of accounting for image-charge effects when modeling transport through molecular junctions

Impulsive correction to the elastic moduli obtained using the stress-fluctuation formalism in systems with truncated pair potential

The truncation of a pair potential at a distance r_cut is well-known to imply in general an impulsive correction to the pressure and other moments of the first derivatives of the potential. That depending on r_cut the truncation may also be of relevance to higher derivatives is shown theoretically for the Born contributions to the elastic moduli obtained using the stress-fluctuation formalism in d dimensions. Focusing on isotropic liquids for which the shear modulus G must vanish by construction, the predicted corrections are tested numerically for binary mixtures and polydisperse Lennard-Jones beads in, respectively, d=3 and d=2 dimensions

Large tunable image-charge effects in single-molecule junctions

The characteristics of molecular electronic devices are critically determined by metal-organic interfaces, which influence the arrangement of the orbital levels that participate in charge transport. Studies on self-assembled monolayers (SAMs) show (molecule-dependent) level shifts as well as transport-gap renormalization, suggesting that polarization effects in the metal substrate play a key role in the level alignment with respect to the metal's Fermi energy. Here, we provide direct evidence for an electrode-induced gap renormalization in single-molecule junctions. We study charge transport in single porphyrin-type molecules using electrically gateable break junctions. In this set-up, the position of the occupied and unoccupied levels can be followed in situ and with simultaneous mechanical control. When increasing the electrode separation, we observe a substantial increase in the transport gap with level shifts as high as several hundreds of meV for displacements of a few \aa ngstroms. Analysis of this large and tunable gap renormalization with image-charge calculations based on atomic charges obtained from density functional theory confirms and clarifies the dominant role of image-charge effects in single-molecule junctions

Two phase transitions in the fully frustrated XYXY model

The fully frustrated $XY$ model on a square lattice is studied by means of Monte Carlo simulations. A Kosterlitz-Thouless transition is found at $T_{\rm KT} \approx 0.446$, followed by an ordinary Ising transition at a slightly higher temperature, $T_c \approx 0.452$. The non-Ising exponents reported by others, are explained as a failure of finite size scaling due to the screening length associated with the nearby Kosterlitz-Thouless transition.Comment: REVTEX file, 8 pages, 5 figures in uuencoded postscrip