Dielectric ordering of water molecules arranged in a dipolar lattice

Abstract

Intermolecular hydrogen bonds impede long-range (anti-)ferroelectric order of water. We confine H 2 O molecules in nanosized cages formed by ions of a dielectric crystal. Arranging them in channels at a distance of~5 Å with an interchannel separation of~10 Å prevents the formation of hydrogen networks while electric dipole-dipole interactions remain effective. Here, we present measurements of the temperature-dependent dielectric permittivity, pyrocurrent, electric polarization and specific heat that indicate an order-disorder ferroelectric phase transition at T 0 ≈ 3 K in the water dipolar lattice. Ab initio molecular dynamics and classical Monte Carlo simulations reveal that at low temperatures the water molecules form ferroelectric domains in the ab-plane that order antiferroelectrically along the channel direction. This way we achieve the long-standing goal of arranging water molecules in polar order. This is not only of high relevance in various natural systems but might open an avenue towards future applications in biocompatible nanoelectronics.

Protein dielectrophoresis: Key dielectric parameters and evolving theory

“…Finally, implicit in Matyushov's theory and our empirical model is the possibility that the anomalously large DEP polarizability of solvated proteins is associated with a large effective dielectric permittivity ( ε eff = κε m ). This could resemble a so‐called relaxor ferroelectric state, which can be regarded as a nano‐ordered ferroelectric with a smeared‐out diffusive phase transition [71]. Supportive evidence for the existence of such nanodomains in the hydration shell of lysozyme has been obtained in MD simulations reported by Martin and Matyushov [98].…”

“…Even a small perturbation of an applied field could result in infinite polarization and ferroelectric behavior. Clausius had considered this possibility in 1879, and only recently has this possibility been treated seriously, e.g., [69] and experimentally demonstrated [71].…”

Single-particle and collective excitations of polar water molecules confined in nano-pores within a cordierite crystal lattice

“…27–31 The existence of various types of dipolar orderings of H 2 O molecules has been predicted theoretically or demonstrated by computer simulations; however, until recently, no robust experimental observation under ambient conditions has been reported. 32–42 However, in a very recent study 43 we were able to demonstrate that such a state indeed can be formed when single water molecules are confined in cages existing within the crystalline lattice of cordierite, a beryl-related compound.…”

“…Their dipole moments are aligned along the c -axis due to coupling of the molecules to alkali ions located at channel bottlenecks.) In our previous work, 43 we presented results of broad-band dielectric spectroscopic studies of the temperature-dependent dielectric response of water molecules in the cordierite matrix. In the present study, we provide additional dielectric and specific heat data and analyses.…”

Unusual features of lattice dynamics in lawsonite related to its phase transitions: a study using broad-band dielectric spectroscopy

“…This behavior is generally linked to the appearance of ferroelectricity; however, as its value of Curie temperature T C = −20 K is negative, hydrated beryl ranks among incipient ferroelectrics where the dipole ordering cannot be realized. Interestingly, more recent analogous investigations on hydrated cordierite 11 have revealed an order-disorder ferroelectric phase transition of the water molecules occurring below 3 K.…”