A new approach to the evaluation of Casimir and van der Waals forces in the transition region

This paper studies the incorporation of Casimir and van der Waals forces applied to a nanostructure with parallel configuration. The focus of this study is in a transition region in which Casimir force gradually transforms into van der Waals force. It is proposed that in the transition region, a proportion of both Casimir and van der Waals forces, as the interacting nanoscale forces, can be considered based on the separation distance between upper structure and substrate during deflection. Moreover, as the separation distance descends during deflection, the nanoscale forces could transform from Casimir to a proportion of both Casimir and van der Waals forces and so as to van der Waals. This is also extended to the entire surface of the nanostructure in such a way that any point of the structure may be subjected to Casimir, van der Waals or a proportion of both of them about its separation distance from the substrate. Therefore, a mathematical model is presented which calculate the incorporation of Casimir and van der Waals forces considering transition region and their own domination area. The mechanical behavior of a circular nano-plate has been investigated as a case study to illustrate how different approaches to nanoscale forces lead to different results. For this purpose, the pull-in phenomena and frequency response in terms of magnitude have been studied based on Eringen nonlocal elasticity theory. The results are presented using different values of the nonlocal parameter and indicated in comparison with those of the classical theory. These results also amplify the idea of studying the mechanical behavior of nanostructures using the nonlocal elasticity theory.     

A self-consistent approach for modelling the interfacial properties and phase diagrams of Yukawa,Lennard-Jones and square-well fluids

A self-consistent density-functional approach is presented for describing the phase behaviour and interfacial tensions of van der Waals fluids represented by the hard-core Yukawa (HCY), Lennard-Jones (LJ) and square-well (SW) potentials. The excess Helmholtz energy functional is formulated in terms of a modified fundamental measure theory (MFMT) for the short-ranged repulsion and a density-gradient expansion for the van der Waals attractions. Analytical expressions for the direct correlation functions of uniform fluids are utilized to take into account the effect of van der Waals’ attraction on intermolecular correlations. For bulk phases, the density functional theory is reduced to an equation of state (EOS) that provides accurate saturation pressures and vapour–liquid phase diagrams. Near the critical region, the long-range fluctuations can be corrected by using the renormalization group (RG) theory. With the same set of molecular parameters, the theory also yields satisfactory surface tensions and interfacial density profiles at all relevant temperatures.     

Graphene on Ir(111): physisorption with chemical modulation

The nonlocal van der Waals density functional approach is applied to calculate the binding of graphene to Ir(111). The precise agreement of the calculated mean height h = 3.41 ? of the C atoms with their mean height h = (3.38±0.04) ? as measured by the x-ray standing wave technique provides a benchmark for the applicability of the nonlocal functional. We find bonding of graphene to Ir(111) to be due to the van der Waals interaction with an antibonding average contribution from chemical interaction. Despite its globally repulsive character, in certain areas of the large graphene moiré unit cell charge accumulation between Ir substrate and graphene C atoms is observed, signaling a weak covalent bond formation.     

Wetting of Alkanes on Water from a Cahn-Type Theory: Effects of Long-Range Forces

We apply the phenomenological wetting theory of Cahn to fluids with van der Waals forces, and in particular to the wetting of pentane on water. Taking into account explicitly the long-range substrate–adsorbate interaction allows us to reproduce the experimentally observed critical wetting transition, which arises from the vanishing of the Hamaker constant at T53°C. This transition is preceded by a first-order transition between a thin and a thick film at a (much) lower temperature. If long-range forces are neglected, this thin–thick transition is the only wetting transition and critical wetting is missed. Our study focuses on the development of useful theoretical tools, such as phase portraits and interface potentials adapted to systems with van der Waals forces.     

Van der Waals forces in electrolyte solutions

In this article we study van der Waals forces in electrolyte solutions from a local point of view. It is shown for arbitrary geometry that the classical limit of the force density exerted on the ions, as found in the macroscopic theory of van der Waals forces, is identical with the force density calculated from electrostatics and thermodynamic fluctuation theory. Thus neither retardation, nor the Lorentz force affect the average force density.     

Nuclear magnetic shielding and diamagnetic susceptibility of interacting hydrogen atoms

A quantum-mechanical study is made of the changes of the nuclear magnetic screening constant σ and the diamagnetic susceptibility X of two interacting hydrogen atoms due to van der Waals and overlap interatomic forces (effects of electron spin being neglected). At large distances the calculations show that van der Waals forces decrease the nuclear screening but increase the diamagnetic susceptibility (in magnitude). As the internuclear distance is reduced the first effect of overlap forces is to increase the screening in the repulsive (electronic triplet) state but this is followed by a further reduction. Attractive overlap forces (as in the ground state of H₂) ultimately lead to an increase in screening.     

Force spectroscopy in noncontact mode

We have analyzed the possibility of using noncontact scanning force microscopy (NCAFM) to detect variations in surface composition, i.e., to detect a ‘spectroscopic image' of the sample. This ability stems from the fact that the long-range forces, acting between the AFM tip and sample, depend on the composition of the AFM tip and sample. The long-range force can be magnetic, electrostatic, or van der Waals forces. Detection of the first two forces is presently used in scanning force microscopy technique, but van der Waals forces have not been used. We demonstrate that the recovery of spectroscopic image has a unique solution. Furthermore, the spectroscopic resolution can be as good as lateral one.     

Comparison study of exchange-correlation functionals on prediction of ground states and structural properties

Despite significant advances in first-principles calculation methods, there is no single exchange-correlation functional which predicts the ground state of materials without an error yet. We investigated how accurately ground states of binary semiconductors are described using 16 exchange-correlation functionals (with or without van der Waals corrections). LDA, PBEsol, SCAN (with or without rVV10 correction), and PBE with D3 van der Waals correction (zero or Becke-Johnson damping) show good predicting power. The lattice constants of stable phases were slightly better described by SCAN, PBEsol, PBE+D3 (Becke-Johnson damping), and MS2. We also propose a set of functionals to double-check the stability of new materials based on the majority vote.     

Hydrogen bonds and van der waals forces in ice at ambient and high pressures

The first principles methods, density-functional theory and quantum Monte Carlo, have been used to examine the balance between van der Waals (vdW) forces and hydrogen bonding in ambient and high-pressure phases of ice. At higher pressure, the contribution to the lattice energy from vdW increases and that from hydrogen bonding decreases, leading vdW to have a substantial effect on the transition pressures between the crystalline ice phases. An important consequence, likely to be of relevance to molecular crystals in general, is that transition pressures obtained from density-functional theory exchange-correlation functionals which neglect vdW forces are greatly overestimated.     

Effect of interparticle forces on the coagulation of ultrafine SiO2 particles

The mechanism of ultrafine (<100 nm) SiO₂ particle production under thermal arc plasma conditions is studied by modelling. Two cases of the process are considered in the model: (i) when it is determined as a pure free-molecular coagulation; (ii) when the coagulation is influenced by the interparticle forces. The Hamaker formula is used to present the van der Waals forces between the particles. Particle size distribution functions (PSDF) are calculated for both cases. It is shown that inclusion of the interparticle interactions does not affect the self-preservation of the PSDF. The mean particle sizes are obtained from the PSDF and compared. Higher values are observed in the case that includes van der Waals forces. Comparison between experimental and calculated PSDF shows better agreement in the case considering interparticle forces.     

The boundary element approach to Van der Waals interactions

We develop a boundary element method to calculate Van der Waals interactions for systems composed of domains of spatially constant dielectric response of a general boundary shape. We achieve this by rewriting the interaction energy expression presented in Phys. Rev. B, 62 (2000) 6997 exclusively in terms of surface integrals of surface operators. We validate this approach in the Lifshitz case and give numerical results for the interaction of two spheres as well as the van der Waals self-interaction of a uniaxial ellipsoid. Our method is simple to implement and is particularly suitable for a full, non-perturbative numerical evaluation of non-retarded van der Waals interactions between objects of a completely general shape.     

External forces outside of a layered electron gas

We calculate the external forces outside of the surface of a layered electron gas (LEG). The LEG is a model of a metal where the electrical current is carried in parallel layers, and there is no current between layers. It describes the high-temperature cuprate superconductors and many other layered solids. We calculate the image potential from an external charge, the van der Waals potential from a neutral atom and the Casimir force between the parallel surfaces of two LEGs. Our theory does not use dielectric functions. We write down the quantum mechanical Hamiltonian, calculate the exact ground state energy and deduce the forces from the energy. We also show that the LEG has no surface plasmon.     

Tip and surface properties from the distance dependence of tip-surface interactions

Macroscopic "background" interactions, such as van der Waals and electrostatic forces, determine the frequency change in non-contact atomic force microscopy (NC-AFM). We demonstrate that by analysing the distance dependence of these interactions one can extract more information about the tip radius, charge and chemical composition, as well as about the surface charging and conductivity. For this purpose we calculate the interaction of different NC-AFM tips with a charged and neutral CaF₂ (111) surface and with an ideal metal surface. Force versus distance curves demonstrate a remarkably different behaviour, especially at long distances, dependent on whether the tip is conductive, oxidised or charged. Comparison with experimental curves proves that this analysis can predict tip properties.     

Van der waals waves in free-surface liquids

It is shown that, along with gravity waves, surface and internal waves caused by van der Waals forces may exist in a liquid with a horizontal free surface. A dispersion relation is found by using the stepwise approximation for the coefficients of a wave equation derived for these waves. The surface waves are similar to surface gravity waves in dispersion and amplitude distribution but differ in frequency by several orders of magnitude. Another sequence of roots in the spectrum corresponds to internal van der Waals waves that have an upper frequency bound and the dispersion law typical of a multimode waveguide.     

Formation of a Wave Structure on the Surface of a Graphene Film

A wavy structure of the surface of graphene nanoparticles on a hydrocarbon substrate has been obtained. It has been shown that the wavy surface is the manifestation of the Kelvin-Helmholtz instability at the interface between liquid paraffin and graphene suspension with the inhomogeneity length λ = 250 nm. The manifestation of such wavy structures is due primarily to van der Waals forces.

     

Quantum friction

We investigate the van der Waals friction between graphene and an amorphous SiO(2) substrate. We find that due to this friction the electric current is saturated at a high electric field, in agreement with experiment. The saturation current depends weakly on the temperature, which we attribute to the quantum friction between the graphene carriers and the substrate optical phonons. We calculate also the frictional drag between two graphene sheets caused by van der Waals friction, and find that this drag can induce a voltage high enough to be easily measured experimentally.     

Acceleration of canonical molecular dynamics simulations using macroscopic expansion of the fast multipole method combined with the multiple timestep integrator algorithm

A canonical molecular dynamics (MD) simulation was accelerated by using an efficient implementation of the multiple timestep integrator algorithm combined with the periodic fast multiple method (MEFMM) for both Coulombic and van der Waals interactions. Although a significant reduction in computational cost has been obtained previously by using the integrated method, in which the MEFMM was used only to calculate Coulombic interactions (Kawata, M., and Mikami, M., 2000, 98, J. Comput. Chem., in press), the extension of this method to include van der Waals interactions yielded further acceleration of the overall MD calculation by a factor of about two. Compared with conventional methods, such as the velocity-Verlet algorithm combined with the Ewald method (timestep of 0.25 fs), the speedup by using the extended integrated method amounted to a factor of 500 for a 100 ps simulation. Therefore, the extended method reduces substantially the computational effort of large scale MD simulations.     

二苯甲酮晶体的红外反射光谱研究

室温下记录了有机非线性光学晶体二苯甲酮三种不同偏振的红外反射光谱（２００－４０００ｃｍ＾－１）。利用Ｋ－Ｋ变换确定了晶格振动模的模，纵频率。根据由Ｋ－Ｋ变换得到的介电常数和折射率的色散曲线外推得到晶体的静态介电常数，高频介电常数和近红外波段的折射率。还对反射带进行了认定。研究表明该晶体二苯甲酮分子间不存在氩键，只以弱的范德华键相结合。结合晶体结构对强反射带出现的原因作了解释。     

Unraveling the stability of polypeptide helices: critical role of van der Waals interactions

Folding and unfolding processes are important for the functional capability of polypeptides and proteins. In contrast with a physiological environment (solvated or condensed phases), an in?vacuo study provides well-defined "clean room" conditions to analyze the intramolecular interactions that largely control the structure, stability, and folding or unfolding dynamics. Here we show that a proper consideration of van der Waals (vdW) dispersion forces in density-functional theory (DFT) is essential, and a recently developed DFT+vdW approach enables long time-scale ab?initio molecular dynamics simulations at an accuracy close to "gold standard" quantum-chemical calculations. The results show that the inclusion of vdW interactions qualitatively changes the conformational landscape of alanine polypeptides, and greatly enhances the thermal stability of helical structures, in agreement with gas-phase experiments.