In view of the vital role of water in chemical and physical processes, an exact knowledge of its dielectric function over a large frequency range is important. In this article we report on currently available measurements of the dielectric function of water at room temperature (25 • C) across the full electromagnetic spectrum: microwave, IR, UV and X-ray (up to 100 eV). We provide parameterisations of the complex dielectric function of water with two Debye (microwave) oscillators and high resolution of IR and UV/X-ray oscillators. We also report dielectric parameters for ice-cold water with a microwave/IR spectrum measured at 0.4 • C, while taking the UV spectrum from 25 • C (assuming negligible temperature dependence in UV). We illustrate the consequences of the model via calculations of van der Waals interactions of gas molecules near water surfaces, and an assessment of the thickness of water films on ice and ice films on water. In contrast to earlier models of ice-cold water, we predict that a micron-scale layer of ice is stabilised on a bulk water surface. Similarly, the van der Waals interaction promotes complete freezing rather than supporting a thin premelting layer of water on a bulk ice surface. Density-based extrapolation from warm to cold water of the dielectric function at imaginary frequencies is found to be satisfactory in the microwave but poor (40% error) at IR frequencies.
In this article we analyze the Casimir-Polder interaction of atoms with a solid grating and an additional repulsive interaction between the atoms and the grating in the presence of an external laser source. The combined potential landscape above the solid body is probed locally by diffraction of Bose-Einstein condensates. Measured diffraction efficiencies reveal information about the shape of the Casimir-Polder interaction and allow us to discern between models based on a pairwisesummation (Hamaker) approach and Lifshitz theory.
Theories for the effective polarisability of a small particle in a medium are presented using different levels of approximation: we consider the virtual cavity, real cavity and the hard-sphere models as well as a continuous interpolation of the latter two. We present the respective hard-sphere and cavity radii as obtained from density-functional simulations as well as the resulting effective polarisabilities at discrete Matsubara frequencies. This enables us to account for macroscopic media in van der Waals interactions between molecules in water and their Casimir-Polder interaction with an interface.
According to the classical Archimedes' principle ice floats in water and has a fraction of its volume above the water surface. However, for very small ice particles, other competing forces such as van der Waals forces due to fluctuating charge distributions and ionic forces due to salt ions and charge on the ice surface also contribute to the force balance. The latter crucially depend on both the pH of the water and the salt concentration. The role of these forces in governing the initial stages of ice condensation has never been considered. Here we show that small ice particles can only form below an exclusion zone, from 2 nm (in high salt concentrations) up to 1 µm (in pure water at pH 7) thick, under the water surface. This distance is defined by an equilibrium of upwards buoyancy forces and repulsive van der Waals forces. Ionic forces due to salt and ice surface charge push this zone further down. Only after growing to a radius larger than 10 µm will the ice particles eventually float towards the water surface in agreement with the simple intuition based on Archimedes' principle. Our result is the first prediction of observable repulsive van der Waals forces between ice particles and the water surface outside a laboratory setting. We posit that it has consequences on the biology of ice water as we predict an exclusion zone free of ice particles near the water surface which is sufficient to support the presence of bacteria.
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