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.

At air-water interfaces, the Lifshitz interaction by itself does not promote ice growth. On the contrary, we find that the Lifshitz force promotes the growth of an ice film, up to 1-8 nm thickness, near silica-water interfaces at the triple point of water. This is achieved in a system where the combined effect of the retardation and the zero frequency mode influences the short-range interactions at low temperatures, contrary to common understanding. Cancellation between the positive and negative contributions in the Lifshitz spectral function is reversed in silica with high porosity. Our results provide a model for how water freezes on glass and other surfaces. DOI: 10.1103/PhysRevB.95.155422 Although water in its different forms has been studied for a very long time, several properties of water and ice remain uncertain and are currently under intense investigation [1][2][3][4]. The question we want to address in the present paper is to what extent the fluctuation-induced Lifshitz interaction can promote the growth of ice films at water-solid interfaces, at the triple point of water. Particles and surfaces, e.g., quartz, soot, or bacteria, in supercooled water are known experimentally to nucleate ice formation [5][6][7]. Here, we focus on interfaces between water and silica-based materials and examine the roles of several intervening factors in the sum over frequency modes (Matsubara terms) contributing to the Lifshitz free energy.Quantum fluctuations in the electromagnetic field result in van der Waals interactions, which in their unretarded form were explained by London in terms of frequency-dependent responses to the fluctuations in the polarizable atoms constituting the material medium [8]. The understanding of these interactions was revolutionized when Casimir introduced retardation effects [9]. The theory was later generalized by Lifshitz to include dielectric materials [10,11]. The Lifshitz formula in Eq. (1), derived for three-layer planar geometries [11], gives the interaction energy between two semi-infinite dielectric media described by their frequency-dependent dielectric permittivities as well as the dielectric permittivity of the medium separating them (see Fig. 1).The purpose of the present work is twofold. First, we want to show that a finite size ice film, nucleated by a solid-water interface, can be energetically favorable even when only the Lifshitz interaction is accounted for. Second, we want to highlight a relevant contribution from the zero frequency term in the expression for the Lifshitz energy in a region where it is not expected to be important. The temperature dependence * Mathias.A.Bostrom@ntnu.no † prachi.parashar@ntnu.no ‡ iver.h.brevik@ntnu.no of the Casimir force between metal surfaces [11][12][13][14] relies strongly on the exact behavior of the low-frequency dielectric function of metals. These and many other investigations have provided support for the notion that the zero frequency term would only be relevant at high temperatures or large surface separations at a moderate ...

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.