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.     

Long-range interactions in polymer melts: the anti-Casimir effect

It is well known that small neutral particles normally tend to aggregate due to the van der Waals forces. We discover a new universal long-range interaction between solid objects in polymer media that is directly opposite the van der Waals attraction. The new force could reverse the sign of the net interaction, possibly leading to the net repulsion. This universal repulsion comes from the subtracted soft fluctuation modes, which are not present in the real polymer system, but rather are in its ideal counterpart. The predicted effect has a deep relation to the classical Casimir interactions, providing an unusual example of fluctuation-induced repulsion instead of normal attraction. That is why it is referred to as the anti-Casimir effect. We also find that the correlation function of monomer units in a concentrated solution of infinite polymer chains follows a power-law rather than an exponential decay at large distances.     

The role of van der Waals interaction in the tilted binding of amine molecules to the Au(111) surface

We present the results of ab initio electronic structure calculations for the adsorption characteristics of three amine molecules on Au(111), which show that the inclusion of van der Waals interactions between the isolated molecule and the surface leads in general to good agreement with experimental data on the binding energies. Each molecule, however, adsorbs with a small tilt angle (between -5 and 9°). For the specific case of 1,4-diaminobenzene (BDA) our calculations reproduce the larger tilt angle (close to 24°) measured by photoemission experiments, when intermolecular (van der Waals) interactions (for about 8% coverage) are included. These results point not only to the important contribution of van der Waals interactions to molecule-surface binding energy, but also that of intermolecular interactions, often considered secondary to that between the molecule and the surface, in determining the adsorption geometry and pattern formation.     

Harmonic dynamical behaviour of thallous halides

Harmonic dynamical behaviour of thallous halides (TlCl and TlBr) have been studied using the new van der Waals three-body force shell model (VTSM), which incorporates the effects of the van der Waals interaction along with long-range Coulomb interactions, three-body interactions and short-range second neighbour interactions in the framework of rigid shell model (RSM). Phonon dispersion curves (PDC), variations of Debye temperature with absolute temperature and phonon density of state (PDS) curves have been reported for thallous halides using VTSM. Comparison of experimental values with those of VTSM and TSM are also reported in the paper and a good agreement between experimental and VTSM values has been found, from which it may be inferred that the incorporation of van der Waals interactions is essential for the complete harmonic dynamical behaviour of thallous halides.     

Molecular forces caused by the confinement of thermal noise

We have investigated spontaneous surface instabilities of very thin polymer films. Film stability and the wavelength of the dominating unstable mode were found to depend sensitively on the media adjacent to the film. Our experimental results cannot be explained by van der Waals interactions alone. To account for the presence of an additional destabilizing force, we propose that the geometrical confinement of thermally excited acoustic waves gives rise to a force that is strong enough to destabilize thin films. This thermoacoustic effect is of similar magnitude as van der Waals 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.     

范德瓦尔斯磁性材料CrOCl变磁性相变的磁力显微镜研究

近年来,二维范德瓦尔斯磁性材料因为在自旋电子学的应用前景而吸引了广泛的关注.CrOCl是一种范德瓦尔斯磁性材料,理论预言其单层具有高达160 K的居里温度,因此吸引了广泛的关注。为了更好的理解这一材料的磁性,我们利用磁力显微镜研究了CrOCl变磁性相变中磁畴结构随磁场的变化。实验发现,在2K下CrOCl样品表面出现随磁场变化的方格条纹,给出了变磁性相比中反铁磁相和铁磁相竞争的图样,并通过二维快速傅里叶变换证实了CrOCl磁性的各向异性。我们的结果为后续研究CrOCl薄层的磁性提供了参考依据。     

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.     

What controls the thickness of wetting layers near bulk criticality?

We study the thickness of wetting layers in the binary-liquid mixture cyclohexane methanol. Far from the bulk critical point, the wetting layer thickness is independent of temperature, resulting from the competition between van der Waals and gravitational forces. Upon approaching the bulk critical temperature [t=(T(c)-T)/T(c)-->0], we observe that the wetting layer thickness diverges as t(-beta) with effective critical exponent beta=0.23+/-0.06. This is characteristic of a broad, intermediate scaling regime for the crossover from van der Waals wetting to critical scaling. We predict beta=beta/3 approximately 0.11, with beta the usual bulk-order parameter critical exponent, showing a small but significant difference with experiment.     

Mechanical effect of van der waals interactions observed in real time in an ultracold Rydberg gas

We present time-resolved spectroscopic measurements of Rydberg-Rydberg interactions between two Rydberg atoms in an ultracold gas, revealing the pair dynamics induced by long-range van der Waals interactions between the atoms. By detuning the excitation laser, a specific pair distribution is prepared. Penning ionization on a microsecond time scale serves as a probe for the pair dynamics under the influence of the attractive long-range forces. Comparison with a Monte Carlo model not only explains all spectroscopic features but also gives quantitative information about the interaction potentials. The results imply that the interaction-induced ionization rate can be influenced by the excitation laser. Surprisingly, interaction-induced ionization is also observed for Rydberg states with purely repulsive interactions.     

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.     

Cross-Over Between First-Order and Critical Wetting at the Liquid-Vapour Interface of n-Alkane/Methanol Mixtures: Tricritical Wetting and Critical Prewetting

A simple mean-field theory is presented which describes the basic observations of recent experiments revealing rich wetting behaviour of n-alkane/methanol mixtures at the liquid-vapour interface. The theory, qualitative and in part heuristic, is based on a microscopic lattice-gas model from which a Cahn–Landau approach is distilled. Besides the physics associated with the short-range components of the intermolecular interactions, effects of the long-range tails of the net van der Waals forces between interfaces are also taken into account. Further, gravitational thinning of the wetting phase is incorporated. The calculation of the spreading coefficient S is extended to the experimentally relevant situation in which the bulk adsorbate is slightly away from two-phase coexistence due to gravity. Analysis of this novel approximation to S for systems with short-range forces leads to the conclusion that the surface specific heat exponents _s =1,1/2, and 0, for first-order wetting, tricritical wetting and critical wetting, respectively, are robust with respect to (weak) gravitational thinning, consistently with experiment. For three different systems the adsorption is calculated as a function of temperature and compared with the experimentally measured ellipticity. Including weak long-range forces which favour wetting in the theory does not visibly alter the critical wetting transition for the nonane/methanol mixture, in contrast with the generic expectation of first-order wetting for such systems, but in good agreement with experiment. For decane/methanol weak long-range forces bring the transition very close to the prewetting critical point, leading to an adsorption behaviour closely reminiscent of short-range tricritical wetting, observed experimentally for alkane chain length between 9.6 and 10. Finally, for undecane/methanol the transition is clearly of first order. First-order wetting is also seen in the experiment.     

Interactions of lanthanide atoms: Comparative ab initio study of YbHe,Yb<Subscript> 2</Subscript> and TmHe,TmYb potentials

The results of high-level ab initio calculations are reported for the interatomic potentials describing YbHe, Yb₂, TmHe and TmYb van der Waals interactions. It is found that the interaction properties of Tm and Yb are very similar and the interaction anisotropy in the TmHe and TmYb complexes is very small. We analyze the long-range behavior of the isotropic and anisotropic interaction potentials and discuss some implications for cold and ultracold atomic collisions of the lanthanide atoms.     

Wetting at a polymer gel–vapor interface; a system not influenced by a long-range van der Waals contribution

The exterior of a cross-linked polymer gel resembles a polymer brush. Such gel including its brush can be swollen by a good solvent. The detachment of the solvent–vapor (L–V) interface from the brush is controlled by the adsorption of polymer segments onto this interface and is to a very good approximation not influenced by long-range van der Waals contributions. A wetting transition in this system coincided with the adsorption–desorption transition for chains onto such L–V interface and has various unusual features. There are several indications that in practice this system should feature a second-order wetting transition.     

Van der Waals interactions between atoms and dispersive surfaces at finite temperature

The long-range interactions between an atomic system in an arbitrary energy level and dispersive surfaces in thermal equilibrium at non-zero temperature are revisited within the framework of the quantum-mechanical linear response theory, using generalized susceptibilities for both atom and electromagnetic field. After defining the observables of interest, one presents a general analysis of the atomic level shift valid for any number and form of dielectric surfaces. It is shown that, at zero temperature, one recovers well-known results previously obtained in the linear response regime. The case of a plane dispersive surface is elaborated on in the non-retarded regime. Calculations are given in detail for a dielectric surface exhibiting a single polariton resonance. Theoretical predictions are presented within a physical viewpoint allowing one to discriminate between the various interaction processes: on one hand, the level shift induced by non-resonant quantum fluctuations, on the other hand, two potentially resonant atom-surface couplings. The first resonant process appears for excited-state atoms and originates in an atomic de-excitation channel resonantly coupled to the surface polariton mode. It exists also at zero temperature, and has been studied and observed previously. The second physical process, which exists at non-zero temperature only, corresponds to the reverse process in which a thermal quantum excitation of a surface polariton resonantly couples to an atomic absorption channel. This novel phenomenon is predicted as well for a ground state atom, and can turn the ordinary long-range van der Waals attraction of atoms into a surface repulsion at increasing temperatures. This opens the way to the control and engineering of the sign and amplitude of van der Waals forces via surface temperature adjustment.     

Triple-point wetting on rough substrates

The influence of substrate roughness on the wetting scenario of adsorbed van der Waals films is investigated by theory and experiment. Calculating the bending free energy penalty of a solid sheet picking up the substrate roughness, we show that a finite roughness always leads to triple-point wetting reducing the widths of the adsorbed solid films considerably as compared to that of smooth substrates. Testing the theory against our experimental data for molecular hydrogen adsorbed on gold, we find quantitative agreement.     

Van der Waals interactions and Photoelectric Effect in Noncommutative Quantum Mechanics

We calculate the long-range Van der Waals force and the photoelectric cross section in a noncommutative setup. It is argued that non-commutativity effects could not be discerned for the Van der Waals interactions. The result for the photoelectric effect shows deviation from the usual commutative one, which in principle can be used to put bounds on the space-space non-commutativity parameter.     

Improved van der Waals potentials for alkali halide crystals

Improved values of the van der Waals energy coefficients are presented for 16 alkali halides using more recent electronic polarizabilities and, for each ion, three alternative values of the effective number of electrons. The statistical method of calculating interionic potentials is used to obtain the correlation energy at small interionic separations and the values are scaled to fit the van der Waals energy at large separation. The resultant correlation energy as a function of interionic separation is fitted to both a cubic polynomial and a cr^?6 analytic form. The extent to which the van der Waals interactions are quenched by ionic overlap is derived and contrasted with Catlow et al. work on this effect.