Detachment force of particles with pinning of contact line from fluid bubbles/droplets

Deformation of a spherical droplet or bubble, containing a pair of particles on its surface is considered when equal but opposite forces are applied to the particles. The particles are placed opposite each other thus providing a symmetrical problem which is more amenable to analytical treatment. We extend our previous calculations, concerning such arrangements with constant contact angles, to situations where now it is the contact line that is pinned on the surface of the particles. The force-displacement curves are calculated as the particles are pulled apart and was found to be linear for small displacements. However, it is also found that the "Hookean constant" for the pinned contact line problem is different to one derived for systems with a constant contact angle, being larger if the pinned line is at the equator of the particles

Detachment force of particles from fluid droplets

We calculate the deformation of a spherical droplet, resulting from the application of a pair of opposite forces to particles located diametrically opposite at the two ends of the droplet. The free-energy analysis is used to calculate the force–distance curves for the generated restoring forces, arising from the displacement of the particles relative to each other. While the logarithmic dependence of the “de Gennes–Hooke” constant on the particle to droplet size ratio, ν, is rather well known in the limit of very small ν, we find that for more realistic particle to droplet size ratios, i.e. ν = 0.001 to 0.01, the additional constant terms of O(1) constitute a significant correction to previously reported results. We derive the restoring force constant to be 2πγ[0.5 − ln(ν/2)]−1, in perfect agreement with the exact semi-numerical analysis of the same problem. The deviation from the linear force–displacement behaviour, occurring close to the point of detachment, is also investigated. A study of the energy dissipated shows it to be an increasingly dominant component of the work done during the detachment of the particles, as ν decreases. This indicates the existence of a significantly higher energy barrier to desorption of very small particles, compared to the one suggested by their adsorption energy alone. The influence of the line tension on the detachment force is also considered. It is shown that where line tension is important, the contact angle is no longer a constant but instead alters with the displacement of the particles from their equilibrium positions

Contribution of H-bond vibrations to heat capacity of water

The origin of the anomalously large value of the heat capacity of liquid water is discussed. Comparing the temperature dependence of the heat capacities for water with those for argon and hydrogen sulfide, we separate contributions of the translational and rotational degrees of freedom. The residual part is considered as being caused by the specific contributions of the transversal vibrations of H-bonds. The estimate for the number of H-bonds per molecule is obtained from the analysis of this contribution. This estimate is in quite good agreement with the estimates which follow from the analysis of the specific volume, heat of evaporation, and kinematic shear viscosity

The influence of the liquid slab thickness on the planar vapor–liquid interfacial tension

One of the long standing challenges in molecular simulation is the description of interfaces. On the molecular length scale, finite size effects significantly influence the properties of the interface such as its interfacial tension, which can be reliably investigated by molecular dynamics simulation of planar vapor-liquid interfaces. For the Lennard-Jones fluid, finite size effects are examined here by varying the thickness of the liquid slab. It is found that the surface tension and density in the center of the liquid region decreases significantly for thin slabs. The influence of the slab thickness on both the liquid density and the surface tension is found to scale with 1/S^3; in terms of the slab thickness S, and a linear correlation between both effects is obtained. The results corroborate the analysis of A. Malijevsky, G. Jackson, J. Phys.: Condens. Matter 24 (2012) 464121, who recently detected an analogous effect for the surface tension of liquid nanodroplets