Interplay between proton ordering and ferroelectric polarization in H-bonded KDP-type crystals

The origin of ferroelectricity in KH2PO4 (KDP) is studied by first-principles electronic structure calculations. In the low-temperature phase, the collective off-centre ordering of the protons is accompanied by an electronic charge delocalization from the near and localization at the far oxygen within the O-H...O bonds. Electrostatic forces. then, push the K+ ions towards off-centre positions, and induce a macroscopic polarization. The analysis of the correlation between different geometrical and electronic quantities, in connection with experimental data. supports the idea that the role of tunnelling in isotopic effects is irrelevant. Instead, geometrical quantum effects appear to play a central role. (C) 2001 Elsevier Science B.V. All rights reserved.

First-principles study of ferroelectricity and isotope effects in H-bonded KH2PO4 crystals

By means of extensive first-principles calculations we studied the ferroelectric phase transition and the associated isotope effect in KH2PO4 (KDP). Our calculations revealed that the spontaneous polarization of the ferroelectric phase is due to electronic charge redistributions and ionic displacements which are a consequence of proton ordering, and not vice versa. The experimentally observed double-peaked proton distribution in the paraelectric phase cannot be explained by a dynamics of only protons. This requires, instead, collective displacements within clusters that include also the heavier ions. These tunneling clusters can explain the recent evidence of tunneling obtained from Compton scattering measurements. The sole effect of mass change upon deuteration is not sufficient to explain the huge isotope effect. Instead, we find that structural modifications deeply connected with the chemistry of the H bonds produce a feedback effect on tunneling that strongly enhances the phenomenon. The resulting influence of the geometric changes on the isotope effect agrees with experimental data from neutron scattering. Calculations under pressure allowed us to analyze the issue of universality in the disappearance of ferroelectricity upon compression. Compressing DKDP so that the distance between the two peaks in the deuteron distribution is the same as for protons in KDP, corresponds to a modification of the underlying double-well potential, which becomes 23 meV shallower. This energy difference is what is required to modify the O-O distance in such a way as to have the same distribution for protons and deuterons. At the high pressures required experimentally, the above feedback mechanism is crucial to explain the magnitude of the geometrical effect.

Local and semilocal density functional computations for crystals of 1-alkyl-3-methyl-imidazolium salts

The accuracy and reliability of popular density functional approximations for the compounds giving origin to room temperature ionic liquids have been assessed by computing the T=0 K crystal structure of several 1-alkyl-3-methyl-imidazolium salts. Two prototypical exchange-correlation approximations have been considered, i.e., the local density approximation (LDA) and one gradient corrected scheme [PBE-GGA, Phys. Rev. Lett. 77, 3865 (1996)]. Comparison with low-temperature x-ray diffraction data shows that the equilibrium volume predicted by either approximations is affected by large errors, nearly equal in magnitude (~10%), and of opposite sign. In both cases the error can be traced to a poor description of the intermolecular interactions, while the intramolecular structure is fairly well reproduced by LDA and PBE-GGA. The PBE-GGA optimization of atomic positions within the experimental unit cell provides results in good agreement with the x-ray structure. The correct system volume can also be restored by supplementing PBE-GGA with empirical dispersion terms reproducing the r-6 attractive tail of the van der Waals interactions.

Dispersing Light with Surface Plasmon Polaritonic Crystals

Spectral dispersion of light on a finite-size surface plasmon polaritonic (SPP) crystal has been studied. The angular wavelength separation of one or more orders of magnitude higher than in other state-of-the-art wavelength-splitting devices available to date has been demonstrated. The two-stage process is responsible for the dispersion value, which involves conversion of the incident light into SPP Bloch modes of a nanostructure followed by the SPP Bloch waves refraction at the SPP crystal boundary. The high spectral dispersion achievable in plasmonic devices may be useful for integrated high-resolution spectroscopy in nanophotonic, optical communication and lab-on-a-chip applications.

Existence of multibreathers in one-dimensional Debye crystals

The existence of highly localized multisite oscillatory structures (discrete multibreathers) in a nonlinear Klein-Gordon chain which is characterized by an inverse dispersion law is proven and their linear stability is investigated. The results are applied in the description of vertical (transverse, off-plane) dust grain motion in dusty plasma crystals, by taking into account the lattice discreteness and the sheath electric and/or magnetic field nonlinearity. Explicit values from experimental plasma discharge experiments are considered. The possibility for the occurrence of multibreathers associated with vertical charged dust grain motion in strongly coupled dusty plasmas (dust crystals) is thus established. From a fundamental point of view, this study aims at providing a rigorous investigation of the existence of intrinsic localized modes in Debye crystals and/or dusty plasma crystals and, in fact, suggesting those lattices as model systems for the study of fundamental crystal properties.

Nonlinear dynamics and solitons in Debye bi-crystals

The nonlinear dynamics of longitudinal dust lattice waves propagating in a dusty plasma bi-crystal is investigated. A “diatomic”-like one-dimensional dust lattice configuration is considered, consisting of two distinct dust grain species with different charges and masses. Two different frequency dispersion modes are obtained in the linear limit, namely, an optical and an acoustic wave dispersion branch. Nonlinear solitary wave solutions are shown to exist in both branches, by considering the continuum limit for lattice excitations in different nonlinear potential regimes. For this purpose, a generalized Boussinesq and an extended Korteweg de Vries equation is derived, for the acoustic mode excitations, and their exact soliton solutions are provided and compared. For the optic mode, a nonlinear Schrödinger-type equation is obtained, which is shown to possess bright- (dark-) type envelope soliton solutions in the long (short, respectively) wavelength range. Optic-type longitudinal wavepackets are shown to be generally unstable in the continuum limit, though this is shown not to be the rule in the general (discrete) case.

Nanoscale ferroelectrics machined from single crystals

This paper summarises some of the most recent work that has been done on nanoscale ferroelectrics as a result of a joint collaborative research effort involving groups in Queen's University Belfast, the University of Cambridge and the University of St. Andrews. Attempts have been made to observe fundamental effects of reduced size, and increasing morphological complexity, on ferroelectric behaviour by studying the functional response and domain characteristics in nanoscale single crystal material, whose size and morphology have been defined by Focused Ion Beam (FIB) patterning. This approach to nanoshape fabrication has allowed the following broad statements to be made: (i) in single crystal BaTiO3 sheets, permittivity and phase transition behaviour is not altered from that of bulk material down to a thickness of similar to 75 nm; (ii) in single crystal BaTiO3 sheets and nanowires changes in observed domain morphologies are consistent with large scale continuum modeling.

Thin film capacitor cut from single crystals using focused ion beam milling

The focused ion beam microscope (FIB) has been used to fabricate thin parallel-sided ferroelectric capacitors from single crystals of BaTiO3 and SrTiO3. A series of nano-sized capacitors ranging in thickness from similar to660 nm to similar to300 nm were made. Cross-sectional high resolution transmission electron microscopy (HRTEM) revealed that during capacitor fabrication, the FIB rendered around 20 nm of dielectric at the electrode-dielectric interface amorphous, associated with local gallium impregnation. Such a region would act electrically in series with the single crystal and would presumably have a considerable negative influence on the dielectric properties. However, thermal annealing prior to gold electrodes deposition was found to fully recover the single crystal capacitors and homogenise the gallium profile. The dielectric testing of the STO ultra-thin single crystal capacitors was performed yielding a room temperature dielectric constant of similar to300, as is the case in bulk. Therefore, there was no evidence of a collapse in dielectric constant associated with thin film dimensions.

Clusters, liquids and crystals of dialkylimidazolium salts. A combined perspective from ab initio computer simulations

We summarize results obtained by a combination of ab initio and classical computer simulations of dialkylimidazolium ionic liquids in different states of aggregation, from crystals to liquids and clusters. Unusual features arising from the competition between electrostatic, dispersion, and hydrogen-bonding interactions are identified at the origin of observed structural patterns. We also discuss the way Brønsted acids interact with ionic liquids leading to the formation of hydrogen-bonded anions.

Phase agile reflectarray cells based on liquid crystals

Experimental results at X-band are used to compare the electromagnetic scattering from a printed reflectarray cell, which is constructed on 500 mu m thick layers of three different nematic state liquid crystals. It is shown that a small voltage can be used to vary the permittivity of the tunable substrate and thereby control the phase of the reflected signals. Numerical results using Ansoft HFSS are compared with the measured phase, resonant frequencies and signal attenuation for two orientations of the liquid crystal molecules. Data fitting is employed to quantify the loss tangent and the permittivity values of the three anisotropic specimens. The performance trade-offs that are imposed by the use of commercially available materials are discussed, and the computer model is used to specify the electrical properties of a liquid crystal mixture, which can provide a signal loss of <1 dB and a dynamic phase range of 300 degrees from the patch elements at 10 GHz.