Water is characterized by large molecular electric dipole moments and strong interactions between molecules; however, hydrogen bonds screen the dipole–dipole coupling and suppress the ferroelectric order. The situation changes drastically when water is confined: in this case ordering of the molecular dipoles has been predicted, but never unambiguously detected experimentally. In the present study we place separate H2O molecules in the structural channels of a beryl single crystal so that they are located far enough to prevent hydrogen bonding, but close enough to keep the dipole–dipole interaction, resulting in incipient ferroelectricity in the water molecular subsystem. We observe a ferroelectric soft mode that causes Curie–Weiss behaviour of the static permittivity, which saturates below 10 K due to quantum fluctuations. The ferroelectricity of water molecules may play a key role in the functioning of biological systems and find applications in fuel and memory cells, light emitters and other nanoscale electronic devices.
In our recent work [Bunkin et al. Water 2013, 4, 129-154] it was first obtained that the water layer, having a size of several tens of micrometers and being adjacent to the swollen Nafion interface, is characterized by enhanced optical density; the refractive index of water at the interface is 1.46. Furthermore, the birefringence effect was observed in this layer. To explain these results, it has been hypothesized that because of "disentangling" of charged polymer chains from the Nafion surface toward the bulk of water, a photonic crystal close to the surface is formed [Bunkin et al. Water 2013, 4, 129-154]. In this paper, we describe experiments with laser-stimulated luminescence from dry and swollen Nafion. It was shown in the experiment with dry Nafion that the apparatus function of our experimental setup (Green's function) is well-described by a Gaussian profile. It was obtained that a highly concentrated colloidal suspension of Nafion particles with a steep spatial boundary is formed in the water layer adjacent to the interface. The volume density of the Nafion particles as a function of the distance from the Nafion interface was found. These findings can be considered indirect confirmation of the previously formulated photonic crystal hypothesis [Bunkin et al. Water 2013, 4, 129-154].
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