Macroscopic Dipole Moment Research Articles

Electrode process of mobile ions in generating space-charge polarization.

Macroscopic dipole moments formed in electrolytic cells influence dielectric properties of the cells, and their magnitudes can be quantified by dielectric spectroscopy. We analyze the dielectric spectra observed for dilute electrolytic cells in low-frequency regions from two perspectives: space-charge polarization and diffuse double layers on the electrodes. The difference between the two polarization phenomena is characterized by the effective dielectric constant and the kinetic parameter introduced in the Poisson-Nernst-Planck model. The analytical results indicate that the generation of space-charge polarization is attributed to the kinetic process of mobile ions replacing solvent molecules on the electrode surface. This is an experimental confirmation of the formation process of macroscopic dipole moment due to space-charge polarization and its practical contribution to the dielectric constant of material.

Symmetry and reactivity of π-systems in electric and magnetic fields: a perspective from conceptual DFT.

The extension of conceptual density-functional theory (conceptual DFT) to include external electromagnetic fields in chemical systems is utilised to investigate the effects of strong magnetic fields on the electronic charge distribution and its consequences on the reactivity of π-systems. Formaldehyde, H2CO, is considered as a prototypical example and current-density-functional theory (current-DFT) calculations are used to evaluate the electric dipole moment together with two principal local conceptual DFT descriptors, the electron density and the Fukui functions, which provide insight into how H2CO behaves chemically in a magnetic field. In particular, the symmetry properties of these quantities are analysed on the basis of group, representation, and corepresentation theories using a recently developed automatic program for symbolic symmetry analysis, QSYM2. This allows us to leverage the simple symmetry constraints on the macroscopic electric dipole moment components to make profound predictions on the more nuanced symmetry transformation properties of the microscopic frontier molecular orbitals (MOs), electron densities, and Fukui functions. This is especially useful for complex-valued MOs in magnetic fields whose detailed symmetry analyses lead us to define the new concepts of modular and phasal symmetry breaking. Through these concepts, the deep connection between the vanishing constraints on the electric dipole moment components and the symmetry of electron densities and Fukui functions can be formalised, and the inability of the magnetic field in all three principal orientations considered to induce asymmetry with respect to the molecular plane of H2CO can be understood from a molecular perspective. Furthermore, the detailed forms of the Fukui functions reveal a remarkable reversal in the direction of the dipole moment along the CO bond in the presence of a parallel or perpendicular magnetic field, the origin of which can be attributed to the mixing between the frontier MOs due to their subduced symmetries in magnetic fields. The findings in this work are also discussed in the wider context of a long-standing debate on the possibility to create enantioselectivity by external fields.

Signal distortion awakened from optical memory estimated using a calculation method with spatiotemporal separation.

The fidelity of photonic storage and retrieval is an essential criterion in long-distance all-optical network nodes. However, the recovered signals from optical memories based on the photon echo (PE) protocol are accompanied by undesired waveform variation and temporal drift. In this study, we use a numerical calculation method with spatiotemporal separation to investigate the essence of signal distortion. The results show that the asynchronous evolution of the macroscopic population difference and the macroscopic dipole moment with time is responsible for echo signal real distortion caused by phase shifts at the in-phase point of the recorded information. The constructive interference of the dipoles at the moment of reaching the in-phase point induces the photon emission, and this point with a nonspecific phase will be naturally accompanied by waveform changes, a small amount of time advance and delay of the PE signal, which is actually a false signal distortion. Such radiation mechanism of the inhomogeneous broadening media provides a perspective to accurately and correctly recognize the temporal drift and waveform variation of the recovered optical signal.

Universality of Dicke superradiance in arrays of quantum emitters

Dicke superradiance is an example of emergence of macroscopic quantum coherence via correlated dissipation. Starting from an initially incoherent state, a collection of excited atoms synchronizes as they decay, generating a macroscopic dipole moment and emitting a short and intense pulse of light. While well understood in cavities, superradiance remains an open problem in extended systems due to the exponential growth of complexity with atom number. Here we show that Dicke superradiance is a universal phenomenon in ordered arrays. We present a theoretical framework – which circumvents the exponential complexity of the problem – that allows us to predict the critical distance beyond which Dicke superradiance disappears. This critical distance is highly dependent on the dimensionality and atom number. Our predictions can be tested in state of the art experiments with arrays of neutral atoms, molecules, and solid-state emitters and pave the way towards understanding the role of many-body decay in quantum simulation, metrology, and lasing.

A model for dynamical solvent control of molecular junction electronic properties

Experimental measurements of electron transport properties of molecular junctions are often performed in solvents. Solvent-molecule coupling and physical properties of the solvent can be used as the external stimulus to control the electric current through a molecule. In this paper, we propose a model that includes dynamical effects of solvent-molecule interaction in non-equilibrium Green's function calculations of the electric current. The solvent is considered as a macroscopic dipole moment that reorients stochastically and interacts with the electrons tunneling through the molecular junction. The Keldysh-Kadanoff-Baym equations for electronic Green's functions are solved in the time domain with subsequent averaging over random realizations of rotational variables using the Furutsu-Novikov method for the exact closure of infinite hierarchy of stochastic correlation functions. The developed theory requires the use of wideband approximation as well as classical treatment of solvent degrees of freedom. The theory is applied to a model molecular junction. It is demonstrated that not only electrostatic interaction between molecular junction and solvent but also solvent viscosity can be used to control electrical properties of the junction. Alignment of the rotating dipole moment breaks the particle-hole symmetry of the transmission favoring either hole or electron transport channels depending upon the aligning potential.

Long-Lasting Molecular Orientation Induced by a Single Terahertz Pulse.

We present a novel, previously unreported phenomenon appearing in a thermal gas of nonlinear polar molecules excited by a single THz pulse. We find that the induced orientation lasts long after the excitation pulse is over. In the case of symmetric-top molecules, the time-averaged orientation remains indefinitely constant, whereas in the case of asymmetric-top molecules the orientation persists for a long time after the end of the pulse. We discuss the underlying mechanism, study its nonmonotonous temperature and amplitude dependencies, and show that there exist optimal parameters for maximal residual orientation. The persistent orientation implies a long-lasting macroscopic dipole moment, which may be probed by even harmonic generation and may enable deflection by inhomogeneous electrostatic fields.

Investigation of Plasma Oscillations in Glasslike Dielectrics by Means of Total External Reflection of X Rays

Glasslike dielectrics are investigated by methods of plasmon dispersion and asymmetry of the number of localized electrons in the region in which total external reflection of X-rays is formed and excitation of plasmon oscillations takes place. The internal mechanical stress and the related polarization of the studied dielectrics are determined. It is discovered that a lithium fluoride crystal lacks an internal mechanical stress and that the observed polarization in this single crystal is caused by a large macroscopic dipole moment.

Исследование плазменных колебаний в стеклообразных диэлектриках методом полного внешнего отражения рентгеновских лучей

Glass-like dielectrics are studied by methods of plasmon dispersion and asymmetry of the number of localized electrons in the zone of formation of the total external reflection of x-rays and the excitation of plasma vibrations. Defined by the internal mechanical stress and the associated polarization of the investigated dielectrics. The absence of internal mechanical stress in a single crystal of lithium fluoride was found out, and the observed polarization is caused by a large macroscopic dipole moment in this single crystal

Thermal illusion with the concept of equivalent thermal dipole

The research on thermal illusion contributes to both fundamental theories and practical applications. In the existing literatures, the most common mechanism is to design a shell to disguise the inside core. However, the core-shell scheme may be weak to handle many-particle systems because N particles may require N specially-designed shells. This lacks efficiency and restricts practical applications. To solve this problem, we can no longer focus on the local effect of a single particle. In contrast, we should study the macroscopic effect of the N particles by treating each particle as an equivalent thermal dipole. Then, thermal illusion can be achieved when the macroscopic equivalent thermal dipole moments of different systems are equal to each other. This requires only once calculation and contributes to efficiency. Accidentally, the concept of equivalent thermal dipole helps to revisit the well-known Bruggeman theory and provides a clear physical image for it. The proposed scheme is verified by theoretical analyses, finite-element simulations, and laboratory experiments. Our work offers an efficient approach to achieving thermal illusion in many-particle systems, and contributes to potential applications in misleading infrared detection, manipulating heat flux, etc.

Continuous SiCN Fibers with Interfacial SiC xN y Phase as Structural Materials for Electromagnetic Absorbing Applications.

SiCN ceramics are one of the most important electromagnetic wave (EMW) absorbing materials for application in harsh environments, but research studies on optimizing phase distribution in SiCN ceramics for excellent EMW absorbing properties are still lacking. Herein, continuous SiCN fibers with an interfacial SiC xN y phase were prepared through nanochannel diffusion-controlled nitridation of polycarbosilane fibers with an NH3 gas flow. The existence of the interfacial SiC xN y phase distributed between the carbon-rich SiC phase and Si3N4 phase can improve the impedance matching and efficiently promote the production of macroscopic dipole moments in the heterointerfaces of SiC xN y-SiC and SiC xN y-Si3N4 for an enhanced multifarious polarization relaxation loss. The EMW absorption properties can be further improved by optimizing the microstructure with a continuous carbon-rich SiC phase for possessing an excellent conductive loss by converting the EMW energy into current flow. Finally, under the synergy of the interfacial SiC xN y phase and the continuous carbon-rich SiC phase, SiCN fibers can present excellent EMW absorption properties with extremely strong absorption ability (reflection loss of -63.7 dB), ultrathin thickness (1.78 mm), and wide effective absorption bandwidth (4.20 GHz). These obtained SiCN fibers also possess excellent mechanical properties with the tensile strength higher than 2.0 GPa and excellent high-temperature stability up to 1500 °C. This work provides a strategic method for optimizing the microstructure of SiCN ceramics for admirable EMW absorption properties, and the obtained SiCN fibers can be used as reinforcements of ceramic matrix composites for stealth applications under harsh environments.

High vacuum equipment for the measurement of the macroscopic dipole moment of polar molecular crystals.

Polar crystals placed into a charged plate capacitor may experience a mechanical torque. Mounting crystals on a spiral spring allows us to measure the momentum and thus the macroscopic dipole moment of a crystal object. To exclude the influence of ambient conditions (air, ions, electrons), experiments are performed in a high vacuum. Following text book knowledge, polar crystals show a surface charge density especially for faces involving the polar crystal axis. For ambient conditions, it is assumed that external charge carriers compensate the surface charge. Here, we present unique equipment by which the dipole moment of crystals can be measured also when the charge carrying parts of a crystal were cut off by two metallic blades. Present measurements for α-resorcinol (mm2) allow us to conclude that (a) as grown polar crystals measured under the high vacuum condition show a macroscopic dipole moment, (b) the weighted dipole moment increases after cutting the main polar faces, and (c) the weighted dipole moment decreased after exposure to ambient air.

Theory of the vortex-clustering transition in a confined two-dimensional quantum fluid

Clustering of like-sign vortices in a planar bounded domain is known to occur at negative temperature, a phenomenon that Onsager demonstrated to be a consequence of bounded phase space. In a confined superfluid, quantized vortices can support such an ordered phase, provided they evolve as an almost isolated subsystem containing sufficient energy. A detailed theoretical understanding of the statistical mechanics of such states thus requires a microcanonical approach. Here we develop an analytical theory of the vortex clustering transition in a neutral system of quantum vortices confined to a two-dimensional disk geometry, within the microcanonical ensemble. As the system energy increases above a critical value, the system develops global order via the emergence of a macroscopic dipole structure from the homogeneous phase of vortices, spontaneously breaking the Z2 symmetry associated with invariance under vortex circulation exchange, and the rotational SO(2) symmetry due to the disk geometry. The dipole structure emerges characterized by the continuous growth of the macroscopic dipole moment which serves as a global order parameter, resembling a continuous phase transition. The critical temperature of the transition, and the critical exponent associated with the dipole moment, are obtained exactly within mean-field theory. The clustering transition is shown to be distinct from the final state reached at high energy, known as supercondensation. The dipole moment develops via two macroscopic vortex clusters and the cluster locations are found analytically, both near the clustering transition and in the supercondensation limit. The microcanonical theory shows excellent agreement with Monte Carlo simulations, and signatures of the transition are apparent even for a modest system of 100 vortices, accessible in current Bose-Einstein condensate experiments.

Effects of nitrogen dopants on the atomic step kinetics and electronic structures of O-polar ZnO.

Oxygen-polar ZnO films are grown in step flow mode by molecular beam epitaxy. Driven by the step flow anisotropy, the growth leads to the occurrence of specific hexagonal pits in the surface. The specific pits are formed by interlacing steps of the {10̄1̄4} facets, thus quenching the macroscopic dipole moment along the c-axis and satisfying the stabilization principles. Nitrogen (N) doping trials are then performed on the basis of the stable surface. In doping, growth remains in step flow mode but the step flow anisotropy vanishes, resulting in an obvious change of the surface morphology. Besides, a distinct acceptor state appears by in situ scanning tunneling spectroscopy analysis. First-principles calculations reveal that N readily substitutes for step-edge Zn and acts as NO2 adsorbed at the step edge. Desorption of the NO2 facilitates the formation of NO-VZn shallow acceptor complexes, which contributes to the appearance of the acceptor state. According to the peculiarities of N dopants on the O-polar surface, vicinal O-polar substrates (e.g., {10̄1̄4} substrate) are promising in ZnO : N due to the easily achieved step flow growth and high density of step edges for N incorporation.

First-Principles Investigation of the Electronic Properties and Stabilities of the LaAlO3 (001) and (110) (1 × 1) Polar Terminations

The first-principles thermodynamics characterization of the stabilities and electronic properties of the LaAlO3 (001) and (110) polar surfaces was systematically performed using density functional theory methods. Two types of polar surfaces, including the terminations along the (001) orientation (the LaO- and AlO2-terminated surfaces) and the (110) orientation (the LaAlO-, O2-, La-, AlO-, and O-terminated surfaces), were considered in this study. The computational results of the charge redistributions and geometries confirm that the electronic structure change and surface reconstruction should be responsible for the cancellation of the macroscopic dipole moments of these polar terminations, which stabilizes them. The charge neutralization can also be achieved by the charge redistribution of surface atoms. Furthermore, using the surface grand potential method in which the effect of the chemical environment on surface stability is considered, we constructed the stability phase diagram of the LaAlO3 (001) an...

Ferroelectric Bloch-line switching: A paradigm for memory devices?

Vortices inside polar domain walls in ferroelastic materials can form ordered arrays resembling Bloch-lines in magnets. The Bloch lines are energetically degenerate with dipoles oriented perpendicular to the wall. By symmetry, these dipoles are oriented at +90° or −90° relative to the wall dipoles. These two states have the same energy and can be inverted by modest applied electric fields. As the majority of wall dipoles are oriented inside the wall, perpendicular to the Bloch line vortex, weak depolarization fields exist for the wall dipoles but not for Bloch lines. The Bloch line density depends on the density of the twin walls and the elastic anisotropy of the crystal structure. We estimate that distances between twin boundaries are as small as 50 nm and Bloch lines can form with some densities of 100 Bloch lines in an area of 100 × 100 nm2. The local dipole moment in the Bloch line is equivalent to the displacement of Ti in BaTiO3. Switchable Bloch lines can be detected by their macroscopic dipole moment and can constitute the functional part of a memory device.

Quantum Rotor Model for a Bose-Einstein Condensate of Dipolar Molecules

We show that a Bose-Einstein condensate of heteronuclear molecules in the regime of small and static electric fields is described by a quantum rotor model for the macroscopic electric dipole moment of the molecular gas cloud. We solve this model exactly and find the symmetric, i.e., rotationally invariant, and dipolar phases expected from the single-molecule problem, but also an axial and planar nematic phase due to many-body effects. Investigation of the wave function of the macroscopic dipole moment also reveals squeezing of the probability distribution for the angular momentum of the molecules.

Tuning photocatalytic performance of the near-infrared-driven photocatalyst Cu2(OH)PO4 based on effective mass and dipole moment

Recently, Cu2(OH)PO4 was found as the first photocatalyst active in the near-infrared(NIR) region of the solar spectrum (Angew. Chem., Int. Ed., 2013, 52, 4810; Chem. Eng. News, 2013, 91, 36), motivating us to explore systemically its photocatalytic mechanism under near-infrared light and how to improve and tune its photocatalytic performance. Herein, electronic structures, and effective masses of electron and hole at energy band edges are theoretically investigated by employing spin-polarized density functional theory calculations. The calculated energy band structure supports the absorption spectra of Cu2(OH)PO4 in the NIR region corresponding to the electron excitation from the valence band to the unoccupied bands in the gap. Our charge density analysis indicates that the O atoms in the hydroxyl serves as the effective bridge for the favoring separation of the photogenerated electron-hole pairs. Furthermore, the effective masses of electron and hole analysis demonstrate that the separation and transfer of photogenerated carriers along the [011] direction may be more effective than other possible directions. A qualitative comparison of carrier transfer ability along all the directions in the specific planes is displayed by the three-dimensional band structure. Interestingly, the calculated net dipole moment for the two basic units of Cu2(OH)PO4, octahedron and trigonal bipyramid, indicate that the macroscopic dipole moment for Cu2(OH)PO4 is zero, however, the distorted octahedron unit has a net dipole moment, which enables us to tune the macroscopic dipole moment by doping. The present work provides theoretical insight leading to a better understanding of the photocatalytic performance of Cu2(OH)PO4 and it may be beneficial to prepare more efficient Cu2(OH)PO4 for NIR light photocatalysis, which will also be helpful to design and prepare novel photocatalysts.

Properties of contactless and contacted charging in MEMS capacitive switches

The dielectric charging in MEMS capacitive switches is a complex effect. The high electric field during pull-down causes intrinsic free charge migration and dipole orientation as well as charge injection. The macroscopic dipole moment of the first two mechanisms is opposite to the one arising from charge injection. This causes partial compensation hence mitigates the overall charging and increases the device lifetime. The charging due to intrinsic free charge migration and dipole orientation can be monitored under contactless electric field application in the pull-up state. The paper investigates the characteristics of contactless charging and compares them with the ones of contacted charging. The characteristics of the discharging process that follows each charging procedure are also presented.

Polar Switching in Trialkylbenzene-1,3,5-tricarboxamides

The hydrogen-bonded hexagonal columnar LC (Col(hd)) phases formed by benzene-1,3,5-tricarboxamide (BTA) derivatives can be aligned uniformly by an electric field and display switching behavior with a high remnant polarization. The polar switching in three symmetrically substituted BTAs with alkyl chains varying in length between 6 and 18 carbon atoms (C6, C10, and C18) was investigated by electro-optical switching experiments, dielectric relaxation spectroscopy (DRS), and solid-state NMR. The goal was to characterize ferroelectric properties of BTA-based columnar LCs, which display a macroscopic axial dipole moment due to the head-to-tail stacking of hydrogen-bonded amides. The Col(hd) phase of all three BTAs can be aligned uniformly by a dc field ∼30 V/μm. Moreover, C10 and C18 display extrinsic polar switching characterized by a remnant polarization and coercive field of 1-2 μC/cm(2) and 20-30 V/μm, respectively. In the absence of an external field, the polarization is lost in 1-1000 s, depending on device details and temperature. DRS revealed a columnar glass transition in the low-temperature region of the LC phase related to collective vibrations in the hydrogen-bonded columns that freeze out below 41-54 °C. At higher temperatures, a relaxation process is present originating from the collective reorientation of amide groups along the column axis (inversion of the macrodipole). Matching activation energies suggest that the molecular mechanism underlying the polar switching and the R-processes is identical. These results illustrate that LC phases based on BTAs offer the unique possibility to integrate polarization with other functionalities in a single nanostructured material.

Interaction-induced ferroelectricity in the rotational states of polar molecules

We show that a ferroelectric quantum phase transition can be driven by the dipolar interaction of polar molecules in the presence a microwave field. The obtained ferroelectricity crucially depends on the harmonic confinement potential, and the macroscopic dipole moment persists even when the external field is turned off adiabatically. The transition is shown to be second order for fermions and for bosons of a smaller permanent dipole moment, but is first order for bosons of a larger moment. Our results suggest the possibility of manipulating the microscopic rotational state of polar molecules by tuning the trap's aspect ratio (and other mesoscopic parameters), even though the later's energy scale is smaller than the former's by six orders of magnitude.