Van der Waals-corrected density functional theory : benchmarking for hydrogen–nanotube and nanotube–nanotube interactions

Density functional theory (DFT) is a powerful approach to electronic structure calculations in extended systems, but suffers currently from inadequate incorporation of long-range dispersion, or Van der Waals (VdW) interactions. VdW-corrected DFT is tested for interactions involving molecular hydrogen, graphite, single-walled carbon nanotubes (SWCNTs), and SWCNT bundles. The energy correction, based on an empirical London dispersion term with a damping function at short range, allows a reasonable physisorption energy and equilibrium distance to be obtained for H2 on a model graphite surface. The VdW-corrected DFT calculation for an (8, 8) nanotube bundle reproduces accurately the experimental lattice constant. For H2 inside or outside an (8, 8) SWCNT, we find the binding energies are respectively higher and lower than that on a graphite surface, correctly predicting the well known curvature effect. We conclude that the VdW correction is a very effective method for implementing DFT calculations, allowing a reliable description of both short-range chemical bonding and long-range dispersive interactions. The method will find powerful applications in areas of SWCNT research where empirical potential functions either have not been developed, or do not capture the necessary range of both dispersion and bonding interactions.

Interface of graphane with copper : a van der Waals density-functional study

Various forms of hydrogenated graphene have been produced to date by several groups, while the synthesis of pure graphane has not been achieved yet. The study of the interface between graphane, in all its possible hydrogenation configurations, and catalyst metal surfaces can be pivotal to assess the feasibility of direct CVD growth methods for this material. We investigated the adhesion of graphane to a Cu(111) surface by adopting the vdW-DF2-C09 exchange-correlation functional, which is able to describe dispersion forces. The results are further compared with the PBE and the LDA exchange-correlation functionals. We calculated the most stable geometrical configurations of the slab/graphane interface and evaluated how graphane's geometrical parameters are modified. We show that dispersion forces play an important role in the slab/graphane adhesion. Band structure calculations demonstrated that in the presence of the interaction with copper, the band gap of graphane is not only preserved, but also enlarged, and this increase can be attributed to the electronic charge accumulated at the interface. We calculated a substantial energy barrier at the interface, suggesting that CVD graphane films might act as reliable and stable insulating thin coatings, or also be used to form compound layers in conjunction with metals and semiconductors.

Analysis of Parameter Values in the van der Waals and Platteeuw Theory for Methane Hydrates Using Monte Carlo Molecular Simulations

The van der Waals and Platteuw (vdVVP) theory has been successfully used to model the thermodynamics of gas hydrates. However, earlier studies have shown that this could be due to the presence of a large number of adjustable parameters whose values are obtained through regression with experimental data. To test this assertion, we carry out a systematic and rigorous study of the performance of various models of vdWP theory that have been proposed over the years. The hydrate phase equilibrium data used for this study is obtained from Monte Carlo molecular simulations of methane hydrates. The parameters of the vdWP theory are regressed from this equilibrium data and compared with their true values obtained directly from simulations. This comparison reveals that (i) methane-water interactions beyond the first cage and methane-methane interactions make a significant contribution to the partition function and thus cannot be neglected, (ii) the rigorous Monte Carlo integration should be used to evaluate the Langmuir constant instead of the spherical smoothed cell approximation, (iii) the parameter values describing the methane-water interactions cannot be correctly regressed from the equilibrium data using the vdVVP theory in its present form, (iv) the regressed empty hydrate property values closely match their true values irrespective of the level of rigor in the theory, and (v) the flexibility of the water lattice forming the hydrate phase needs to be incorporated in the vdWP theory. Since methane is among the simplest of hydrate forming molecules, the conclusions from this study should also hold true for more complicated hydrate guest molecules.

Emergent photophenomena in three dimensional van der Waals heterostructures

We report on the fabrication and observation of emergent opto-electronic phenomena in three dimensional, micron-sized van der Waals heterostructures self-assembled from atomic layers of graphene and hexagonal boron nitride in varying ratios.

Pull-in Instability Study of Carbon Nanotube Tweezers Under the Influence of Van der Waals Forces

The pull-in instability of two nanotubes under van der Waals force is studied. The cantilever beam with large deformation model is used. The influence of nanotube parameters such as the interior radius, the gap distance between the two nanotubes, etc, on the pull-in instability is studied. The critical nanotube length is determined for each specific set of nanotube parameters. The Galerkin method is applied to discretize the governing equations, and it shows good convergence.

Morphological Stability of Epitaxial Thin Elastic Films by Van Der Waals Force

The morphological stability of epitaxial thin elastic films on a substrate by van der Waals force is discussed. It is found that only van der Waals force with negative Hamaker constant (A < 0) tends to stabilize the film, and the lower bound for the Hamaker constant is also obtained for the stability of thin film. The critical value of the undulation wavelength is found to be a function of both film thickness and external stress. The charateristic time-scale for surface mass diffusion scales to the fourth power to the wavelength of the perturbation.

Combined effect of surface tension, gravity and van der Waals force induced by a non-contact probe tip on the shape of liquid surface

Aiming at understanding how a liquid film on a substrate affects the atomic force microscopic image in experiments, we present an analytical representation of the shape of liquid surface under van der Waals interaction induced by a non-contact probe tip. The analytical expression shows good consistence with the corresponding numerical results. According to the expression, we find that the vertical scale of the liquid dome is mainly governed by a combination of van der Waals force, surface tension and probe tip radius, and is weekly related to gravity. However, its horizontal extension is determined by the capillary length.

Influence of van der Waals and Casimir Forces on Electrostatic Torsional Actuators

The influence of van der Waals (vdW) and Casimir forces on the stability of the electrostatic torsional nanoelectromechanical systems (NEMS) actuators is analyzed in the paper. With the consideration of vdW and Casimir effects, the dependence of the critical tilting angle and pull-in voltage on the sizes of structure is investigated. And the influence of vdW torque is compared with that of Casimir torque. The modified coefficients of vdW and Casimir torques on the pull-in voltage are, respectively, calculated. When the gap is sufficiently small, pull-in can still take place with arbitrary small angle perturbation because of the action of vdW and Casimir torques even if there is not electrostatic torque. And the critical pull-in gaps for two cases are, respectively, derived.

Dynamic Stability of Electrostatic Torsional Actuators with van Der Waals Effect

electrostatic torsional nano-electro-mechanical systems (NEMS) actuators is analyzed in the paper. The dependence of the critical tilting angle and voltage is investigated on the sizes of structure with the consideration of vdW effects. The pull-in phenomenon without the electrostatic torque is studied, and a critical pull-in gap is derived. A dimensionless equation of motion is presented, and the qualitative analysis of it shows that the equilibrium points of the corresponding autonomous system include center points, stable focus points, and unstable saddle points. The Hopf bifurcation points and fork bifurcation points also exist in the system. The phase portraits connecting these equilibrium points exhibit periodic orbits, heteroclinic orbits, as well as homoclinic orbits.