Molecular dynamics simulations are used to study contact between a rigid, nonadhesive, spherical tip with radius of order 30nm and a flat elastic substrate covered with a fluid monolayer of adsorbed chain molecules. Previous studies of bare surfaces showed that the atomic scale deviations from a sphere that are present on any tip constructed from discrete atoms lead to significant deviations from continuum theory and dramatic variability in friction forces. Introducing an adsorbed monolayer leads to larger deviations from continuum theory, but decreases the variations between tips with different atomic structure. Although the film is fluid, it remains in the contact and behaves qualitatively like a thin elastic coating except for certain tips at high loads. Measures of the contact area based on the moments or outer limits of the pressure distribution and on counting contacting atoms are compared. The number of tip atoms making contact in a time interval grows as a power of the interval when the film is present and logarithmically with the interval for bare surfaces. Friction is measured by displacing the tip at a constant velocity or pulling the tip with a spring. Both static and kinetic friction rise linearly with load at small loads. Transitions in the state of the film lead to nonlinear behavior at large loads. The friction is less clearly correlated with contact area than load.
We study the effect of asperity size on the adhesion properties of metal contact using atomistic simulations. The simulated size effect of individual nanoscale asperityies is applied to macroscopic rough surfaces by introducing a curvature radius distribution to a continuum-mechanics-based contact model. Our results indicate that the contact adhesion can be optimized by changing the curvature radius distribution of the asperity summits.
We predict a strongest size for the contact strength when asperity radii of curvature decrease below ten nanometers. The reason for such strongest size is found to be correlated with the competition between the dislocation plasticity and surface diffusional plasticity. The essential role of temperature is calculated and illustrated in a comprehensive asperity size-strengthtemperature map taking into account the effect of contact velocity. Such a map should be essential for various phenomena related to nanoscale contacts such as nanowire cold welding, self-assembly of nanoparticles and adhesive…
It is proposed that lubricant molecules adsorbed on an interface between two asperities in contact, which is rough on the atomic scale, can switch the interface from the strong to weak pinning regime, resulting in a large reduction in the static friction. This is proposed as a possible mechanism for boundary lubrication. \
Atomistic simulations are used to test the equations of continuum contact mechanics in nanometer scale contacts. Nominally spherical tips, made by bending crystals or cutting crystalline or amorphous solids, are pressed into a flat, elastic substrate. The normal displacement, contact radius, stress distribution, friction and lateral stiffness are examined as a function of load and adhesion. The atomic scale roughness present on any tip made of discrete atoms is shown to have profound effects on the results. Contact areas, local stresses, and the work of adhesion change by factors of two to fou…
First-principles simulations were performed to investigate reaction of carbon nanotubes with adsorbed metal atoms. Mechanical modification of their structures enhances chemical reactivity of carbon nanotubes. Adsorption of a tungsten, tantalum, or niobium atom on a (5, 0) nanotube with a Stone-Wales defect was shown to have characteristically strong chemisorption. Bond-breaking in the carbon-carbon network and formation of a local metal-carbon complex were observed during the simulation. Adsorption of W, Ta, Ni or Mo on a twisted (5, 0) nanotube showed a preferred breaking of several bonds, ev…
It is shown that lines of adsorbed hydrogen pair atoms divide the graphene sheet into strips and form hydrogen-based superlattice structures (2HG-SL). We show that the forming of 2HG-SL drastically changes the electronic properties of graphene from semimetal to semiconductor. The electronic spectra of "zigzag" (n,0) 2HG-SL is similar to that of (n,0) carbon nanotubes and have a similar oscillation of band gap with number n, but with non-zero minimal values. The composite dual-periodic (n,0)+(m,0) 2HG-SLs of "zigzag" strips are analyzed, with the conclusion that they may be treated as quasi-two…
Grand canonical Monte Carlo simulations have been performed to determine the adsorption behavior of Ar and Kr atoms on the exterior surface of a rope (bundle) consisting of many carbon nanotubes. The computed adsorption isotherms reveal phase transitions associated with the successive creation of quasi-one dimensional lines of atoms near and parallel to the intersection of two adjacent nanotubes.
In this communication we investigate two dyes N,N' -dioctadecyl thiacyanine perchlorate (NK) and octadecyl rhodamine B chloride (RhB) in Langmuir and Langmuir-Blodgett (LB) films with or with out a synthetic clay laponite. Observed changes in isotherms of RhB in absence and presence of nano-clay platelets indicate the incorporation of clay platelets onto RhB-clay hybrid films. AFM image confirms the incorporation of clay in hybrid films. FRET was observed in clay dispersion and LB films with and without clay. Efficiency of energy transfer was maximum in LB films with clay.
A theoretical study on the rotational dynamics of H2 molecules trapped in the interstitial channels (ICs) of a carbon nanotube bundle is presented. The potential used in this study is modeled as a sum of atom-atom (C-H) van der Waals interactions and electrostatic interactions of the molecule with the surrounding nanotubes.The rotational energy spectra is calculated using a product wave function, where the coupling between translational and rotational modes is treated in a mean-field manner . Molecular dynamics (MD) simulation study was performed for estimating the hydrogen rotational barrier.…
The structures and electron properties of new superlattices formed on graphene by adsorbed hydrogen molecules are theoretically described. It has been shown that superlattices of the (n, 0) zigzag type with linearly arranged pairs of H atoms have band structures similar to the spectra of (n, 0) carbon nanotubes. At the same time, superlattices of the (n, n) type with a "staircase" of adsorbed pairs of H atoms are substantially metallic with a high density of electronic states at the Fermi level and this property distinguishes their spectra from the spectra of the corresponding (n, n) nanotubes…
This paper assesses the importance of three-body triple dipole interactions for quasi-one dimensional phases of He, Ne, H_2, Ar, Kr and Xe confined within interstitial channels or on the external surfaces of nanotube bundles. We find the substrate-mediated contribution to be substantial: for interstitial H_2 the well depth of the effective pair potential is reduced to approximately one half of its value in free space. We carry out ab initio calculations on linear and equilateral configurations of H_2 trimer and find that overlap interactions do not greatly change the DDD interaction in the lin…
We present classical molecular dynamics calculations of the behavior of copper and gold nanoparticles on a graphene sheet, sheared with a constant applied force $F_{\rm a}$. The force $F_{\rm s}$ acting on the particle from the substrate depends on the material of the nanoparticles (Au or Cu), and exhibits a sawtooth dependency on time, which we attribute to local commensurability between the metal nanoparticle surface atomic positions with the graphene lattice. The time-averaged value of $F_{\rm s}$ (the friction force) acting on Au nanoparticles increases linearly with the contact area, havi…
Monte-Carlo simulation technique has been used to investigate the effect of temperature and adsorbed gases on the composition profile of unsupported Pt-Rh nanocatalysts. For a 2406 atom fcc cubo-octahedral Pt$_{\rm{}50}$Rh$_{\rm{}50}$ nanocatalyst the shell-wise composition for all the eight shells has been simulated. For the temperatures 700 K, 1000 K and 1300 K, the top shell of clean Pt-Rh nanocatalysts is found to be mildly Pt-enriched, while the second shell is Pt-depleted. The Pt concentration of the top shell shows a maximum at T = 1000 K. In presence of a quarter monolayer of adsorbed …
We study the role of strong electron confinement in surface-enhanced Raman scattering from molecules adsorbed on small noble-metal particles. We describe a new source of Raman signal enhancement which originates from different behavior of sp-band and d-band electron densities near the particle boundary. In small particles, a spillover of sp-electron wave-functions beyond the classical radius gives rise to a thin layer with diminished population of d-electrons. In this surface layer, the screening of sp-electrons by d-band electron background is reduced. We demonstrate that the interplay betwee…
The Self-Assembly of Nano-Objects (SANO) code we implemented demonstrates the ability to predict the molecular self-assembly of different structural motifs by tuning the molecular building blocks as well as the metallic substrate. It consists in a two-dimensional Grand Canonical Monte-Carlo (GCMC) approach developed to perform atomistic simulations of thousands of large organic molecules self-assembling on metal surfaces. Computing adsorption isotherms at room temperature and spanning over the characteristic sub-micrometric scales, we confront the robustness of the approach with three differen…
We investigated interaction between hydrogen molecules and bare as well as functionalized single-wall carbon nanotubes (SWNT) using first-principles plane wave method. We found that the binding energy of the H$_{2}$ physisorbed on the bare SWNT is very weak, and can be enhanced neither by increasing the curvature of the surface through radial deformation, nor by the coadsorption of Li atom that makes the semiconducting tube metallic. Though the bonding is strengthened upon adsorption directly to Li atom, yet its nature continues to be physisorption. However, the character of the bonding change…
The contact between a liquid and an elastic solid generates a stress vector depending on the curvature tensor in each point of the separating surface. For nanometer values of the mean curvature and for suitable materials, the stress vector takes significant amplitude on the surface. Although the surface average action of the liquid on the solid is the hydrostatic pressure, the local strain generates torques tending to regularize the surface undulations and asperities.
The structural and electronic properties of fluorine (F)-doped BN nanotubes (BNNTs) are studied using density functional methods. Our results indicate that F atoms prefer to substitute N atoms, resulting in substantial changes of BN layers. However, F substitutional doping results in no shallow impurity states. The adsorption of F atoms on B sites is more stable than that on N sites. BNNTs with adsorbed F atoms are p-type semiconductors, suggesting the electronic conduction in F-doped multiwalled BNNTs with large conductivity observed experimentally might be of p-type due to the adsorbed F ato…
The underlying mechanisms responsible for triboelectricity have yet to be completely understood. We have previously proposed a model which explains charge transfer in non-metals via band bending due to electromechanical, especially flexoelectric, effects at deformed asperities coupled with work function differences. Here, we investigate whether the shape of asperities is important for triboelectricity. The results indicate that the shape is important in general, since how the electromechanical response scales with force and asperity size depends on the shape. This is qualitatively in agreement…
Here we show results of first-principles investigations aiming at tuning and controlling the catalytic activity of gold nanoclusters through the design of the underlying support. We show that gold clusters adsorbed on a very thin (2 layers) defect-free MgO film which is itself supported on Mo(100), may serve as model catalysts for the low-barrier oxidation of CO. The origin of the emergent activity of the nanoclusters is a dimensionality crossover of the adsorbed gold clusters, from inactive three-dimensional (3D) optimal structures on thick MgO films, to catalytically active 2D ones for suffi…
A recent exciting experiment by Ghosh et al. reported that the flow of an ion-containing liquid such as water through bundles of single-walled carbon nanotubes induces a voltage in the nanotubes that grows logarithmically with the flow velocity v0. We propose an explanation for this observation. Assuming that the liquid molecules nearest the nanotube form a 2D solid-like monolayer pinned through the adsorbed ions to the nanotubes, the monolayer sliding will occur by elastic loading followed by local yield (stick-slip). The drifting adsorbed ions produce a voltage in the nanotube through electr…
We propose a theoretical model of friction under electrochemical conditions focusing on the interaction of a force microscope tip with adsorbed polar molecules of which the orientation depends on the applied electric field. We demonstrate that the dependence of friction force on the electric field is determined by the interplay of two channels of energy dissipation: (i) the rotation of dipoles and (ii) slips of the tip over potential barriers. We suggest a promising strategy to achieve a strong dependence of nanoscopic friction on the external field based on the competition between long range …
Recent I/V curve measurements suggest that C60 molecules deposited in gold nanojunctions change their adsorption configuration when a finite voltage in a 2-terminal setting is applied. This is of interest for molecular electronics because a robust molecular transistor could be based on such junctions if the mechanism of the process is understood. We present density functional theory based plane wave calculations, where we studied the energetics of the molecule's adsorption under the influence of an external field. Particular emphasis was placed on investigating a possible lightning rod effect …
Surface-state mediated interactions between adsorbates on surfaces can be exploited for the fabrication of self-organized nanostructures such as two-dimensional superlattices of adatoms. Using angle-resolved photoemission we provide experimental evidence that these interactions can be drastically modified by adsorbate-induced alterations in the surface potential barrier. This, in turn, will cause significant changes in the ordering of the adsorbates. For the studied case example of Cs adatoms on Ag(111) our momentum-resolved measurements reveal the surface state Fermi wave vector to be increas…
Long spin relaxation times are a prerequisite for the use of spins in data storage or nanospintronics technologies. An atomic-scale solid-state realization of such a system is the spin of a transition metal atom adsorbed on a suitable substrate. For the case of a metallic substrate, which enables directly addressing the spin by conduction electrons, the experimentally measured lifetimes reported to date are on the order of only hundreds of femtoseconds. Here, we show that the spin states of iron atoms adsorbed directly on a conductive platinum substrate have an astonishingly long spin relaxati…
