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

Recently, the low-temperature phase of water molecules confined within nanocages formed by the crystalline lattice of water-containing cordierite crystals has been reported to comprise domains with ferroelectrically ordered dipoles within the a, b-planes which are antiferroelectrically alternating along the c-axis. In the present work, comprehensive broad-band dielectric spectroscopy is combined with specific heat studies and molecular dynamics and Monte Carlo simulations in order to investigate in more detail the collective modes and single-particle excitations of nanoconfined water molecules. From DFT-MD simulations we reconstruct the potential-energy landscape experienced by the H2O molecules. A rich set of anisotropic temperature-dependent excitations is observed in the terahertz frequency range. Their origin is associated with the complex rotational/translational vibrations of confined H2O molecules. A strongly temperature dependent relaxational excitation, observed at radio-microwave frequencies for the electric field parallel to the crystallographic a-axis, E||a is analyzed in detail. The temperature dependences of loss-peak frequency and dielectric strength of the excitation together with specific heat data confirm a ferroelectric order-disorder phase transition at T0 ≈ 3 K in the network of H2O dipoles. Additional dielectric data are also provided for polarization E||b, too. Overall, these combined experimental investigations enable detailed conclusions concerning the dynamics of the confined water molecules that develop within their microscopic energy landscapes.

Dielectric ordering of water molecules arranged in a dipolar lattice.

Intermolecular hydrogen bonds impede long-range (anti-)ferroelectric order of water. We confine H2O 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 T0 ≈ 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.

Incipient ferroelectricity of water molecules confined to nano-channels of beryl.

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.

Fano resonance and dipolar relaxation in lead-free relaxors.

Fano resonance is a phenomenon in which a discrete state interferes with a continuum of states and has been observed in many areas of science. Here, we report on the prediction of a Fano resonance in ferroelectric relaxors, whose properties are poorly understood: an ab initio molecular dynamic scheme reveals such resonance between the bare optical phonon mode of the Zr sublattice (the discrete state) and the bare optical phonon mode of the Ti sublattice (the continuum of states) in disordered lead-free Ba(Zr,Ti)O3. The microscopic origins of the discrete state and continuum of states are discussed in the context of relaxor properties. Furthermore, our simulations suggest that the T* characteristic temperature of relaxor is related to a hardening of the vibrational frequencies associated with fluctuation of the Ti sublattice. Finally, a terahertz relaxation mode reflecting reorientations of Ti dipoles and showing a thermally activated behaviour is predicted, in agreement with previous experiments.

Broad-band conductivity and dielectric spectroscopy of composites of multiwalled carbon nanotubes and poly(ethylene terephthalate) around their low percolation threshold.

Composites of multiwalled carbon nanotubes with poly(ethylene terephthalate) (PET-MWCNT) with up to 3 vol% MWCNTs were prepared and characterized by broad-band AC conductivity and dielectric spectroscopy up to the infrared range using several techniques. A very low electrical percolation threshold of 0.07 vol% MWCNTs was revealed from the low-frequency conductivity plateau as well as from DC conductivity, whose values show the same critical power dependence on MWCNT concentration with the exponent t = 4.3. Above the plateau, the AC conductivity increases with frequency up to the THz range, where it becomes overlapped with the absorption of vibrational modes. The temperature dependence down to ~5 K has shown semiconductor behaviour with a concentration-independent but weakly temperature-dependent small activation energy of ~3 meV. The behaviour is compatible with the previously suggested fluctuation-induced tunnelling conductivity model through a thin (~1 nm) polymer contact layer among the adjacent MWCNTs within percolated clusters. At higher frequencies, deviations from the simple universal conductivity behaviour are observed, indicating some distribution of energy barriers for an electron hopping mechanism.

Infrared phonon spectroscopy of a compressively strained (001) SrTiO3 film grown on a (110) NdGaO3 substrate.

Polarized infrared reflectivity was measured between 5 and 300 K on a 17 nm thick, 1.1% compressively strained epitaxial (001) SrTiO(3) film and the orthorhombic (110) NdGaO(3) substrate upon which it was grown. A strong in-plane infrared anisotropy of the NdGaO(3) substrate was observed and polar modes with B(1u)-and a mixture of B(2u) + B(3u)-symmetry were seen. At low temperatures three new modes arose in the 90-130 cm( - 1) range, which we assigned to 4f Nd electronic transitions. The in-plane SrTiO(3) film phonons showed strong stiffening compared to the phonon frequencies of bulk unstrained SrTiO(3), particularly the soft mode, and the in-plane phonon peaks were found to split. No anomalies were detected as a function of temperature in either the infrared response or lattice parameters of the compressively strained SrTiO(3) film, providing an absence of evidence for the out-of-plane ferroelectric phase transition predicted by theory.

The negative phonon confinement effect in nanoscopic sodium nitrite.

A nanocomposite of porous glass and a NaNO(2) ferroelectric (channels of approximately 7 nm diameter) was studied using infrared reflectivity, THz transmission and Raman spectroscopy as a function of temperature in the range of 300-500 K, including the ferroelectric transition. From the infrared and THz response the effective dielectric function was calculated and compared with the dielectric functions calculated from the Bruggeman and Lichtenecker models of the effective medium, using the known data on the polar phonon modes of the NaNO(2) single crystals. The results show good qualitative agreement, indicating that the stiffening of the effective modes is due to local depolarization fields on the glass-ferroelectric interfaces. The nonpolar Raman modes show no substantial modification compared to those of the bulk NaNO(2). Some signatures of the ferroelectric transition were even seen. The results indicate that the intrinsic size effect (phonon confinement) is negligible in this nanocomposite.

Broad-band dielectric spectroscopy and ferroelectric soft-mode response in the Ba(0.6)Sr(0.4)TiO(3) solid solution.

Ceramic Ba(0.6)Sr(0.4)TiO(3) (BST-0.6) samples were studied in the broad spectral range of 10(6)-10(14) Hz by using several dielectric techniques in between 20 and 800 K. The dominant dielectric dispersion mechanism in the paraelectric phase was shown to be of strongly anharmonic soft-phonon origin. The whole soft-mode response in the vicinity of the ferroelectric transition was shown to consist of two coupled overdamped THz excitations, which show classical features of a coupled soft and central mode, known from many ferroelectric crystals with a dynamics near the displacive and order-disorder crossover. Similar behaviour has been recently revealed and theoretically simulated in pure BaTiO(3) (see Ponomareva et al 2008 Phys. Rev. B 77 012102 and Hlinka et al 2008 Phys. Rev. Lett. 101 167402). Also for the BST system, this feature was confirmed by the theory based on molecular dynamics simulations with an effective first-principles Hamiltonian. In all the ferroelectric phases, additional relaxation dispersion appeared in the GHz range, assigned to ferroelectric domain-wall dynamics. The microwave losses were analysed from the point of view of applications. The paraelectric losses above 1 GHz are comparable with those in single crystals and appear to be of intrinsic multi-phonon origin. The ceramic BST system is therefore well suited for applications in the whole microwave range.

Coexistence of the phonon and relaxation soft modes in the terahertz dielectric response of tetragonal BaTiO3.

The dielectric response to infrared waves polarized along the tetragonal axis of a ferroelectric single-domain crystal of BaTiO3 was determined by time-domain THz spectroscopy and Fourier-transform infrared reflectivity techniques. In addition to the three well-known polar lattice modes, the experiment shows an additional mode of the relaxation type in the THz spectral region, which accounts for the Curie-Weiss behavior of the c-axis dielectric constant. A comparison of experimental results with ab initio based effective-Hamiltonian simulations allows us to elucidate its relation to the order-disorder model of Comes, Lambert, and Guinier [Solid State Commun. 6, 715 (1968)10.1016/0038-1098(68)90571-1].

The giant electromechanical response in ferroelectric relaxors as a critical phenomenon.

The direct conversion of electrical energy to mechanical work by a material is relevant to a number of applications. This is illustrated by ferroelectric 'relaxors' such as Pb(Mg(1/3)Nb(2/3))O(3)-PbTiO(3) (PMN-PT; refs 5, 6): these materials exhibit a giant electromechanical (piezoelectric) response that is finding use in ultrasonic and medical applications, as well as in telecommunications. The origins of this effect are, however, still unclear. Here we show that the giant electromechanical response in PMN-PT (and potentially other ferroelectric relaxors) is the manifestation of critical points that define a line in the phase diagram of this system. Specifically, in the electric-field-temperature-composition phase diagram of PMN-PT (the composition being varied by changing the PT concentration), a first-order paraelectric-ferroelectric phase transition terminates in a line of critical points where the piezoelectric coefficient is maximum. Above this line, supercritical evolution is observed. On approaching the critical point, both the energy cost and the electric field necessary to induce ferroelectric polarization rotations decrease significantly, thus explaining the giant electromechanical response of these relaxors.

In-plane and out-of-plane ferroelectric instabilities in epitaxial SrTiO3 films.

The in-plane and out-of-plane ferroelectric instabilities in compressed (100)-epitaxial SrTiO3 films were examined by infrared reflection spectroscopy. The strongly stiffened in-plane soft mode frequency softened very slowly on cooling. On the other hand, the silent mode appeared at around 150 K, indicating an out-of-plane ferroelectric transition. This behavior points to a split of in-plane and out-of-plane ferroelectric instability temperatures due to the lowered symmetry of the SrTiO3 lattice caused by mechanical misfit strain. Infrared spectroscopy provides a possibility to detect such an effect in the strained epitaxial ferroelectric films.

Anisotropic dielectric function in polar nanoregions of relaxor ferroelectrics.

The Letter suggests treating the infrared reflectivity spectra of single crystal perovskite relaxors as fine-grained ferroelectric ceramics: locally frozen polarization makes the dielectric function strongly anisotropic in the phonon frequency range and the random orientation of the polarization at nanoscopic scale requires taking into account the inhomogeneous depolarization field. Employing a simple effective medium approximation (the Bruggeman symmetrical formula) turns out to be sufficient for reproducing all principal features of room temperature reflectivity of Pb(Mg(1/3)Nb(2/3))O3. One of the reflectivity bands is identified as a geometrical resonance entirely related to the nanoscale polarization inhomogeneity. The approach provides a general guide for systematic determination of the polar mode frequencies split by the inhomogeneous polarization at the nanometer scale.

Infrared spectroscopy of KTa(1-x)Nb(x)O(3) crystals.

Fourier-transform infrared and time-domain THz dielectric spectroscopy measurements on KTa(1-x)Nb(x)O(3) crystals for x = 0.018 and 0.022 were performed. The temperature behaviour of the soft mode frequency and damping have been determined above the ferroelectric phase transition. No dielectric dispersion in the frequency range below the polar phonon absorption is observed down to kHz frequencies at temperatures from room temperature down to 60 K. At lower temperatures the KTa(1-x)Nb(x)O(3) samples become opaque due to additional losses, which persist down to liquid helium temperatures. This supports the nanoscopic dipolar glassy state rather than macroscopic ferroelectricity at low temperatures.

Soft and central mode behaviour in PbMg(1/3)Nb(2/3)O(3) relaxor ferroelectric.

The relaxor ferroelectric PbMg(1/3)Nb(2/3)O(3) (PMN) is investigated by means of dielectric and Fourier transform far infrared transmission spectroscopy in the frequency range from 10 kHz to 15 THz at temperatures between 20 and 900 K using mostly thin films on infrared transparent sapphire substrates. While the thin film relaxors display reduced dielectric permittivity at low frequencies, their high frequency lattice response is shown to be the same as for single-crystal/ceramic specimens. In contrast to the results of inelastic neutron scattering, the optic soft mode is found to be underdamped at all temperatures. On heating, the TO1 soft phonon follows the Cochran law with an extrapolated critical temperature of 670 K near to the Burns temperature. Above 450 K the soft mode frequency levels off near 50 cm(-1) and above the Burns temperature it slightly hardens. Central-mode-type dispersion assigned to the dynamics of polar nanoclusters appears below the Burns temperature at frequencies near to but below the soft mode and slows down and broadens dramatically on cooling, finally, below the freezing temperature of 200 K, giving rise to frequency independent losses from the microwave range down. A new explanation of the phonon 'waterfall' effect in inelastic neutron scattering spectra is proposed.

Origin of the "waterfall" effect in phonon dispersion of relaxor perovskites.

We have undertaken an inelastic neutron scattering study of the perovskite relaxor ferroelectric Pb(Zn(1/3)Nb(2/3))O3 with 8% PbTiO3 (PZN-8%PT) in order to elucidate the origin of the previously reported unusual kink on the low frequency transverse phonon dispersion curve (known as the "waterfall effect"). We show that its position (q(wf)) depends on the choice of the Brillouin zone and that the relation of q(wf) to the size of the polar nanoregions is highly improbable. The waterfall phenomenon is explained in the framework of a simple model of coupled damped harmonic oscillators representing the acoustic and optic phonon branches.

Severe life-threatening cholera associated with blood group O in Peru: implications for the Latin American epidemic.

A household survey in 1991, at the onset of the Latin American cholera epidemic, investigated high attack rates in Trujillo, Peru, and determined the association between blood group O and severe cholera. Of 463 persons in 69 households, 173 (37%) reported diarrhea, 21% required rehydration therapy, and 4% were hospitalized; these treatment requirements greatly exceeded estimates based on other populations. Elevated vibriocidal or antitoxic antibody titers were present in 52% of 321 from whom serum was obtained; 73% were blood group O. Blood group O was strongly associated with severe cholera: Infected persons had more diarrheal stools per day than persons of other blood groups, were more likely to report vomiting and muscle cramps, and were almost eight times more likely to require hospital treatment. Since prevalence of blood group O in Latin America may be the world's highest, estimates of treatment requirements should be increased to prevent unnecessary deaths.