ABSTRACT
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.
ABSTRACT
Polarized Raman, IR, and time-domain THz spectroscopy of orthorhombic lead zirconate single crystals have yielded a comprehensive picture of temperature-dependent quasiharmonic frequencies of its low-frequency phonon modes. It is argued that these modes primarily involve vibrations of Pb ions and librations of oxygen octahedra. Their relation to phonon modes of the parent cubic phase is proposed. Counts of the observed IR and Raman active modes belonging to distinct irreducible representations agree quite well with group-theory predictions. Analysis of the results yields insight into the phase transition mechanism, involving a soft ferroelectric branch coupled by a trilinear term to another two oxygen octahedra tilt modes.
ABSTRACT
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.
ABSTRACT
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].
ABSTRACT
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.
