Dipolar Liquids Research Articles

Paired correlations of dipolar liquid crystals: A mean-force-potentials approach

Paired correlations of dipolar liquid crystals: A mean-force-potentials approach

Electronic rotons and Wigner crystallites in a two-dimensional dipole liquid.

A key concept proposed by Landau to explain superfluid liquid helium is the elementary excitation of quantum particles called rotons1-8. The irregular arrangement of atoms in a liquid leads to the aperiodic dispersion of rotons, which played a pivotal role in understanding fractional quantum Hall liquids (magneto-rotons)9,10 and the supersolidity of Bose-Einstein condensates11-13. Even for a two-dimensional electron or dipole liquid, in the absence of a magnetic field, the repulsive interactions have been predicted to form a roton minimum14-19, which can be used to trace the transition to Wigner crystals20-24 and superconductivity25-27, although this has not yet been observed. Here, we report the observation of such electronic rotons in a two-dimensional dipole liquid of alkali-metal ions donating electrons to surface layers of black phosphorus. Our data reveal the striking aperiodic dispersion of rotons, which is characterized by a local minimum of energy at finite momentum. As the density of dipoles decreases so that interactions dominate over the kinetic energy, the roton gap reduces to 0, as in a crystal, signalling Wigner crystallization. Our model shows the importance of short-range order arising from repulsion between dipoles, which can be viewed as the formation of Wigner crystallites (bubbles or stripes) floating in the sea of a Fermi liquid. Our results reveal that the primary origin of electronic rotons (and the pseudogap) is strong correlations.

Observation of Bose-Einstein condensation of dipolar molecules.

Ensembles of particles governed by quantum mechanical laws exhibit intriguing emergent behaviour. Atomic quantum gases1,2, liquid helium3,4 and electrons in quantum materials5-7 all exhibit distinct properties because of their composition and interactions. Quantum degenerate samples of ultracold dipolar molecules promise the realization of new phases of matter and new avenues for quantum simulation8 and quantum computation9. However, rapid losses10, even when reduced through collisional shielding techniques11-13, have so far prevented evaporative cooling to a Bose-Einstein condensate (BEC). Here we report on the realization of a BEC of dipolar molecules. By strongly suppressing two- and three-body losses viaenhanced collisional shielding, we evaporatively cool sodium-caesium molecules to quantum degeneracy and cross the phase transition to aBEC. The BEC reveals itself by a bimodal distribution when the phase-space density exceeds 1. BECs with a condensate fraction of 60(10)% and a temperature of 6(2) nK are created and found to be stable with a lifetime close to 2 s. This work opens the door to the exploration of dipolar quantum matter in regimes that have been inaccessible so far, promising the creation of exotic dipolar droplets14, self-organized crystal phases15 and dipolar spin liquids in optical lattices16.

The effect of temperature on permittivity measurements of aqueous solutions of glucose for the development of non-invasive glucose sensors based on electromagnetic waves

This article presents for the first time an empirical study that shows the importance of considering temperature when analyzing the permittivity (dielectric constant) of aqueous glucose solutions of various concentrations. The permittivity is a parameter that is investigated by researchers as a biomarker for non-invasive measurement of glucose without drawing blood. The development of this technology will allow personalized healthcare diagnostics to monitor and prevent diabetes. Since human glucose levels in the blood vary in the range of a few milligrams per decilitre, estimating such small variations of glucose will require a highly accurate and repeatable sensing technology. Electromagnetic (EM) waves, specifically in the microwave and terahertz frequency ranges, have shown promise in detecting changes in the electrical properties of blood plasma as they relate to glucose concentration. However, it's important to note that while this technology shows promise, it is still in the research and development phase. It is shown here that the body temperature can affect the accuracy of the blood glucose measurements. Experiments were conducted with different glucose concentration solutions under various temperatures and the complex permittivity of the glucose was studied across a wide frequency range from 400 MHz to 11 GHz. The rise in thermal energy normally causes dipolar liquids like water to vibrate and rotate disrupting the alignment of the dipoles in response to an electric field thereby reducing its permittivity. Empirical results however show that for aqueous solution of glucose the permittivity increases with rise in temperature from 16 °C to 37 °C. This is attributed to the polar nature of the water and glucose molecules that becomes more pronounced with increased thermal energy. Based on the experimental results an accurate analytical expression is derived that considers the temperature of the aqueous glucose solution. The accuracy of the analytical expression is shown experimentally to be above 99%. The findings from the study should enable the design of accurate non-invasive glucose monitoring devices based on electromagnetic sensing techniques.

Anomalously field-susceptible spin clusters emerging in the electric-dipole liquid candidate κ-(ET)2Hg(SCN)2Br.

Mutual interactions in many-body systems bring about various exotic phases, among which liquid-like states failing to order due to frustration are of keen interest. The organic system with an anisotropic triangular lattice of molecular dimers, κ-(ET)2Hg(SCN)2Br, has been suggested to host a dipole liquid arising from intradimer charge-imbalance instability, possibly offering an unprecedented stage for the spin degrees of freedom. Here, we show that an extraordinary unordered/unfrozen spin state having soft matter-like spatiotemporal characteristics emerges in this system. 1H nuclear magnetic resonance (NMR) spectra and magnetization measurements indicate that gigantic, staggered moments are nonlinearly and inhomogeneously induced by a magnetic field, whereas the moments vanish in the zero-field limit. The analysis of the NMR relaxation rate signifies that the moments fluctuate at a characteristic frequency slowing down to below megahertz at low temperatures. The inhomogeneity, local correlation, and slow dynamics indicative of middle-scale dynamical correlation length of several nanometers suggest novel frustration-driven spin clusterization.

Fracton critical point at a higher-order topological phase transition

The theory of quantum phase transitions separating different phases with distinct symmetry patterns at zero temperature is one of the foundations of modern quantum many-body physics. Here we demonstrate that the existence of a two-dimensional topological phase transition between a higher-order topological insulator (HOTI) and a trivial Mott insulator with the same symmetry eludes this paradigm. We present a theory of this quantum critical point (QCP) driven by the fluctuations and percolation of the domain walls between a HOTI and a trivial Mott insulator region. Due to the spinon zero modes that decorate the rough corners of the domain walls, the fluctuations of the phase boundaries trigger a spinon-dipole hopping term with fracton dynamics. Hence we find that the QCP is characterized by a critical dipole liquid theory with subsystem U(1) symmetry and the breakdown of the area law entanglement entropy which exhibits a logarithmic enhancement: $Lln(L)$. Using the density matrix renormalization group method, we analyze the dipole stiffness together with the structure factor at the QCP, which provides strong evidence of a critical dipole liquid with a Bose surface, UV-IR mixing, and a dispersion relation $\ensuremath{\omega}={k}_{x}{k}_{y}.$

Molecule(s) of Interest: I. Ionic Liquids-Gateway to Newer Nanotechnology Applications: Advanced Nanobiotechnical Uses', Current Status, Emerging Trends, Challenges, and Prospects.

Ionic liquids are a potent class of organic compounds exhibiting unique physico-chemical properties and structural compositions that are different from the classical dipolar organic liquids. These molecules have found diverse applications in different chemical, biochemical, biophysical fields, and a number of industrial usages. The ionic liquids-based products and procedural applications are being developed for a number of newer industrial purposes, and academic uses in nanotechnology related procedures, processes, and products, especially in nanobiotechnology and nanomedicine. The current article overviews their uses in different fields, including applications, functions, and as parts of products and processes at primary and advanced levels. The application and product examples, and prospects in various fields of nanotechnology, domains of nanosystem syntheses, nano-scale product development, the process of membrane filtering, biofilm formation, and bio-separations are prominently discussed. The applications in carbon nanotubes; quantum dots; and drug, gene, and other payload delivery vehicle developments in the nanobiotechnology field are also covered. The broader scopes of applications of ionic liquids, future developmental possibilities in chemistry and different bio-aspects, promises in the newer genres of nanobiotechnology products, certain bioprocesses controls, and toxicity, together with emerging trends, challenges, and prospects are also elaborated.

Contribution of Multiwalled carbon nanotubes to dielectric and elastic properties in E7 nematic liquid crystal

In this article, electrical parameters, and elastic constants of nematic liquid crystal (NLC) contributed multiwalled carbon nanotubes (MCN) are presented by dielectric spectroscopy method. The effects of reorientation on the nematic liquid crystal by doping of multi-walled carbon nanotubes were investigated to reveal. Analyzes of dielectric strength Δε′(ω), absorption coefficient α, relaxation time τ, dielectric anisotropy Δε′V, dielectric anisotropy ratio γ, splay elastic constant K11, and cross-over angular frequency ωco of MCN contribution to E7 nematic liquid crystal with DC supply voltage are presented. Reorientation of elastic dipolar liquid crystal molecules was demonstrated by reducing the positive type (p type) dielectric anisotropy value in the broadband angular frequency range with the MCN contribution to the E7 coded nematic liquid crystal. The supply voltage applied to the NLC samples was observed to have nearly Debye-type relaxation mechanism in the host E7 LC structure, tending to switch to a Debye-type relaxation mechanism by MCN doping. Dipole effects were enhanced by doping of multi-walled carbon nanotubes in the orientation of elastic NLC molecules, and the relaxation time of host E7 NLC and doped MCN/E7 NLC decreased with increasing bias voltages. Cole-Cole analysis with different supply voltages, it has been seen that it turns into a new equivalent circuit depending on the MCN contribution.

Enhanced interactions of interlayer excitons in free-standing heterobilayers.

Strong, long-range dipole-dipole interactions between interlayer excitons (IXs) can lead to new multiparticle correlation regimes1,2, which drive the system into distinct quantum and classical phases2-5, including dipolar liquids, crystals and superfluids. Both repulsive and attractive dipole-dipole interactions have been theoretically predicted between IXs in a semiconductor bilayer2,6-8, but only repulsive interactions have been reported experimentally so far3,9-16. This study investigated free-standing, twisted (51°, 53°, 45°) tungsten diselenide/tungsten disulfide (WSe2/WS2) heterobilayers, in which we observed a transition in the nature of dipolar interactions among IXs, from repulsive to attractive. This was caused by quantum-exchange-correlation effects, leading to the appearance of a robust interlayer biexciton phase (formed by two IXs), which has been theoretically predicted6-8 but never observedbefore in experiments. The reduced dielectric screening in a free-standing heterobilayer not only resulted in a much higher formation efficiency of IXs, but also led to strongly enhanced dipole-dipole interactions, which enabled us to observe the many-body correlations of pristine IXs at the two-dimensional quantum limit. In addition, we firstly observed several emission peaks from moiré-trapped IXs at room temperature in a well-aligned, free-standing WSe2/WS2 heterobilayer. Our findings open avenues for exploring new quantum phases with potential for applications in non-linear optics.

Solvate Ionic Liquids: Assessing the Possibility of Determining the Composition by Means of Gas–Liquid Chromatography

A study is performed of the possibility of using gas–liquid chromatography (GLC) to determine the composition of solutions of lithium salts in aprotic dipolar solvents and solvate ionic liquids. The objects of study are solutions of lithium perchlorate and lithium trifluoromethanesulfonate in sulfolane and solvate complexes of lithium perchlorate with sulfolane obtained in two ways: direct interaction of the initial components in a given molar ratio and interaction of the components in a common solvent with its subsequent removal via evaporation. It is shown that GLC is a convenient way of determining the content of a solvating solvent in the composition of solutions and solvate ionic liquids. The presence of lithium salt in the analyzed solutions does not affect the period of retention; instead, it raises the degree of asymmetry of the chromatographic peak of the solvent and manifestation of the tailing effect. It is found that the presence of salt in the considered system also does not reduce the accuracy of determining the solvent content. The error in determining the content of solvent in solutions of lithium salts and solvate complexes by GLC is no greater than 1%.

Investigation of dielectric relaxation in dipolar liquids from conductivity measurement

Investigation of dielectric relaxation in dipolar liquids from conductivity measurement

Ultradilute Quantum Liquid of Dipolar Atoms in a Bilayer.

We show that ultradilute quantum liquids can be formed with ultracold bosonic dipolar atoms in a bilayer geometry. Contrary to previous realizations of ultradilute liquids, there is no need for stabilizing the system with an additional repulsive short-range potential. The advantage of the proposed system is that dipolar interactions on their own are sufficient for creation of a self-bound state and no additional short-range potential is needed for the stabilization. We perform quantum MonteCarlo simulations and find a rich ground-state phase diagram that contains quantum phase transitions between liquid, solid, atomic gas, and molecular gas phases. The stabilization mechanism of the liquid phase is consistent with the microscopic scenario in which the effective dimer-dimer attraction is balanced by an effective three-dimer repulsion. The equilibrium density of the liquid, which is extremely small, can be controlled by the interlayer distance. From the equation of state, we extract the spinodal density, below which the homogeneous system breaks into droplets. Our results offer a new example of a two-dimensional interacting dipolar liquid in a clean and highly controllable setup.

Non-equilibrium relaxation and aging in the dynamics of a dipolar fluid quenched towards the glass transition

The recently developed non-equilibrium self-consistent generalized Langevin equation theory of the dynamics of liquids of non-spherically interacting particles [2016 J. Phys. Chem. B 120 7975] is applied to the description of the irreversible relaxation of a thermally and mechanically quenched dipolar fluid. Specifically, we consider a dipolar hard-sphere liquid quenched (at t w = 0) from full equilibrium conditions towards different ergodic–non-ergodic transitions. Qualitatively different scenarios are predicted by the theory for the time evolution of the system after the quench (t w > 0), that depend on both the kind of transition approached and the specific features of the protocol of preparation. Each of these scenarios is characterized by the kinetics displayed by a set of structural correlations, and also by the development of two characteristic times describing the relaxation of the translational and rotational dynamics, allowing us to highlight the crossover from equilibration to aging in the system and leading to the prediction of different underlying mechanisms and relaxation laws for the dynamics at each of the glass transitions explored.

Electronic screening using a virtual Thomas-Fermi fluid for predicting wetting and phase transitions of ionic liquids at metal surfaces.

Of relevance to energy storage, electrochemistry and catalysis, ionic and dipolar liquids display unexpected behaviours-especially in confinement. Beyond adsorption, over-screening and crowding effects, experiments have highlighted novel phenomena, such as unconventional screening and the impact of the electronic nature-metallic versus insulating-of the confining surface. Such behaviours, which challenge existing frameworks, highlight the need for tools to fully embrace the properties of confined liquids. Here we introduce a novel approach that involves electronic screening while capturing molecular aspects of interfacial fluids. Although available strategies consider perfect metal or insulator surfaces, we build on the Thomas-Fermi formalism to develop an effective approach that deals with any imperfect metal between these asymptotes. Our approach describes electrostatic interactions within the metal through a 'virtual' Thomas-Fermi fluid of charged particles, whose Debye length sets the screening length λ. We show that this method captures the electrostatic interaction decay and electrochemical behaviour on varying λ. By applying this strategy to an ionic liquid, we unveil a wetting transition on switching from insulating to metallic conditions.

Measuring state-of-order by dielectric response: A comprehensive review on Fröhlich entropy estimation

The so-called Fröhlich entropy is the entropy variation of a material under the application of an electric field. This quantity can be calculated, under suitable hypotheses, from the measured real part of the static dielectric function, when the imaginary part is negligible. Although Fröhlich entropy is defined for a biased sample, a straightforward physical interpretation correlates it to the state-of-order of the considered physical system in absence of field. When Fröhlich entropy is calculated from experimental results, its trend is able to give several information about the evolution in temperature of the explored compound, especially of its phase transition features. We here provide a comprehensive review of the physical systems (dipolar liquids and nematicons, organic molecular crystals, metallic nanoparticles, inorganic disordered ferroelectrics, etc.) where this approach has been exploited with the aim of evaluating their state of order and its temperature evolution. The variety of compounds where this method has been applied demonstrates that the estimation of the Fröhlich entropy can be considered a trustworthy tool for carrying out study on the state-of-order of different classes of materials. Indeed Fröhlich entropy evaluation can be considered a fruitful and reliable investigation technique which can be exploited alongside more usual experimental approaches.

Generic Structural Relaxation in Supercooled Liquids.

One of the unsolved problems of dynamics in supercooled liquids are the differences in spectral shape of the structural relaxation observed among different methods and substances, and a possible generic line shape has long been debated. We show that the light scattering spectra of very different systems, e.g., hydrogen bonding, van der Waals liquids, and ionic systems, almost perfectly superimpose and show a generic line shape of the structural relaxation, following ∝ ω-1/2 at high frequencies. In dielectric spectra the generic behavior is recovered only for systems with low dipole moment, while in strongly dipolar liquids additional cross-correlation contributions mask the generic structural relaxation.

Complexity of the dipolar exciton Mott transition in GaN/(AlGa)N nanostructures

The Mott transition from a dipolar excitonic liquid to an electron-hole plasma is demonstrated in a wide GaN/(Al,Ga)N quantum well at $T=7$K by means of spatially-resolved magneto-photoluminescence spectroscopy. Increasing optical excitation density we drive the system from the excitonic state, characterized by a diamagnetic behavior and thus a quadratic energy dependence on the magnetic field, to the unbound electron-hole state, characterized by a linear shift of the emission energy with the magnetic field. The complexity of the system requires to take into account both the density-dependence of the exciton binding energy and the exciton-exciton interaction and correlation energy that are of the same order of magnitude. We estimate the carrier density at Mott transition as $n_\mathrm{Mott}\approx 2\times 10^{11}$cm$^{-2}$ and address the role played by excitonic correlations in this process. Our results strongly rely on the spatial resolution of the photoluminescence and the assessment of the carrier transport. We show, that in contrast to GaAs/(Al,Ga)As systems, where transport of dipolar magnetoexcitons is strongly quenched by the magnetic field due to exciton mass enhancement, in GaN/(Al,Ga)N the band parameters are such that the transport is preserved up to $9$T.

Thermodynamic properties of a molecular dipolar liquid using the two-phase thermodynamic approach.

A modified version of the original two-phase thermodynamic approach has been extended to evaluate the thermodynamic properties of molecular systems. Its basic assumption states that the density of states can be decomposed into solid-like and gas-like components. The solid part has been approximated by that of a set of harmonic oscillators, whereas a subset composed of rough hard spheres has been considered for the gas part. In this new approach, molecules have been modelled as rotating hard spheres that experience elastic collisions. The technique has been tested on a system made up of dipolar diatomic molecules, and it leads to very good results for total entropy, potential energy reference and heat capacity. Translation and rotation solid components of the overall spectra have been compared to the real part of the instantaneous normal mode vibrational densities of states. Similarities between them reinforce the validity of the two-phase thermodynamic approach.

Long-Range Orientational Organization of Dipolar and Steric Liquids.

Long-range orientational correlations in liquids have received recent renewed interest, in particular for the neat water case. These long-range orientational correlations, exceeding several tens of nanometers, originate from the presence of the strong permanent water dipolar moment. However, the exact dependence with the dipolar moment and the role of other local forces like steric hindrance has never been addressed. In this work, we experimentally measure long-range correlations for a set of liquids differing by their molecular weight and dipolar moment, in order to reveal the origin of their long-range organization. Hence, we show that the dipolar moment of a solvent molecule is not the unique feature determining the orientational correlation. Steric hindrance significantly helps to structure the liquids as well. In order to quantify these long-range correlations, we also derive theoretically the polarization resolved second harmonic scattering intensity as a function of the rotational invariants describing the dipolar and octupolar interaction.

Quantum valence bond ice theory for proton-driven quantum spin-dipole liquids

We present a theory of a hybrid quantum liquid state, $\textit{quantum spin-dipole liquid}$ (QSDL), in a hydrogen-bonded electron system, by combining a quantum proton ice and Anderson's resonating valence bond spin liquid theory, motivated by the recent experimental discovery of a quantum spin liquid with proton fluctuations in $\kappa$-H$_3$(Cat-EDT-TTF)$_2$ (a.k.a. H-Cat). In our theory, an electron spin liquid and a proton dipole liquid are realized simultaneously in the ground state called $\textit{quantum valence bond ice}$. In this state, neither of them can be established independently of the other. Analytical and numerical calculations reveal that this state has a large entanglement entropy between spins and dipoles, which is far beyond the (crude) Born-Oppenheimer approximation. We also examine the stability of QSDL with respect to perturbations and discuss implications for experiments in H-Cat and its deuterated analog D-Cat.