Linear dielectric thermodynamics are formally developed to explore the isothermal and adiabatic temperature - pressure dependence of dielectric constants. The refractive index of optical materials is widely measured in the literature: it is both temperature and pressure dependent. The argument to establish the dielectric constant's isentropic temperature dependence is a thermodynamic one and is thus applicable to all physical models that describe electron clouds and electronic resonances within materials. The isentropic slope of the displacement field versus the electric field at all temperatures is described by an adiabatic dielectric constant in an energy-per-unit mass system. This slope is shown through the electronic part of the entropy to be unstable at high temperatures due to the change in the curvature of the temperature dependence of the dielectric constant. The electronic entropy contribution for optical, thermo-electro materials has negative heat capacities which are unacceptable. The dielectric constant's temperature and pressure dependence is predicted to be only dependent on the specific volume so isentropes are always positive. A new universal form for the dielectric constant follows from this hypothesis: the dielectric constant is proportional to the square root of the specific volume.
A simple description of thermodynamics of DMAAS and DMAGaS ferroelectric crystals by means of Landau expansion is proposed. Conditions of occurrence of phase transitions are established and their temperatures are obtained. The influence of external hydrostatic pressure on phase transitions is described. The temperature behaviour of dielectric susceptibility components and their anomalies in the vicinity of phase transition points are investigated. Obtained results are compared with experimental data.
Within the modified model of proton ordering of one-dimensional ferroelectric having hydrogen bonds of PbHPO$_4$-type, their thermodynamic and dynamic characteristics are studied and calculated taking into account the linear (by crystal deformations $\varepsilon_i$ ($i=1,3$) and $\varepsilon_4$) contributions into the energy of a proton system but without taking into account the tunneling in the two-particle cluster approximation. There has been obtained a good quantitative description of the temperature dependence of polarization, static dielectric permittivity, heat capacity and frequency de…
We present the results of the thermodynamic theory of piezoelectric ferroelectrics and of the phenomenological theory of thermodynamic characteristics of the KH$_{2}$PO$_{4}$ type ferroelectrics. Available experimental data for the dielectric, piezoelectric, and elastic characteristics of the KH$_{2}$PO$_{4}$ type ferroelectrics and NH$_4$H$_{2}$PO$_{4}$ type antiferroelectrics are described using the proposed microscopic theory of these crystals. Using the results of the thermodynamic theory and experimental data we calculate the dielectric, piezoelectric, and elastic characteristics of the K…
Dielectric relaxation has been investigated within the framework of a modified mean field theory, in which the dielectric response of an arbitrary condensed matter system to the applied electric field is assumed to consist of two parts, a collective response and a slowly fluctuating response; the former corresponds to the cooperative response of the crystalline or noncrystalline structures composed of the atoms or molecules held together by normal chemical bonds and the latter represents the slow response of the strongly correlated high-temperature structure precursors or a partially ordered n…
Using first principles calculations, we study the ground-state structure of bulk proton-exchanged lithium niobate, which is also called hydrogen niobate and is widely used in waveguides. Thermodynamics helps to establish the most favorable nonpolar surface as well as the water-deficient and water-rich phases under different ambient conditions, which we refer to as "dehydrated" and "rehydrated" phases, respectively. We compute the low-frequency dielectric response and the optical refractive indices of hydrogen niobate in different phases. The dielectric constant is greatly enhanced compared to …
The fully self-consistent GW approximation is an established method for electronic structure calculations. Its most serious deficiency is known to be an incorrect prediction of the dielectric response. In this work we examine the GW approximation for the homogeneous electron gas and find that problems with the dielectric response are solved by enforcing the particle-number conservation law in the polarization function. Previously reported data for the ground-state energy were plainly contradicting each other well outside of reported error bounds. Some of these results created a false impressio…
It has been considered that polar nanoregions in relaxors form at Burns temperature Td approx 600 K. High-temperature dielectric investigations of Pb(Mg1/3Nb2/3)O3 (PMN) and 0.7PMN-0.3PbTiO3 reveal, however, that the dielectric dispersion around 600 K appears due to the surface-layer contributions. The intrinsic response, analyzed in terms of the universal scaling, imply much higher Td or formation of polar nanoregions in a broad temperature range, while high dielectric constants manifest that polar order exists already at the highest measured temperatures of 800 K. The obtained critical expon…
In the paper, the description of the dielectric and ferroelectric properties of BaTiO_3 single crystals using Landau thermodynamic potential is addressed. Our results suggest that when using the sixth-power free energy expansion of the thermodynamic potential, remarkably different values of the fourth-power coefficient, β(the coefficient of P^4_i terms), are required to adequately reproduce the nonlinear dielectric behavior of the paraelectric phase and the electric field induced ferroelectric phase, respectively. In contrast, the eighth-power expansion with a common set of coefficients enable…
The lacunar spinel GeV4S8 undergoes orbital and ferroelectric ordering at the Jahn-Teller transition around 30 K and exhibits antiferromagnetic order below about 14 K. In addition to this orbitally driven ferroelectricity, lacunar spinels are an interesting material class, as the vanadium ions form V4 clusters representing stable molecular entities with a common electron distribution and a well-defined level scheme of molecular states resulting in a unique spin state per V4 molecule. Here we report detailed x-ray, magnetic susceptibility, electrical resistivity, heat capacity, thermal expansio…
We show that the defect data parameters related to various defect processes, e.g., formation, migration, dielectric relaxation parameters, obey a universal law. In particular, the defect entropies scale with the defect enthalpies irrespective of the process considered. A concrete example is given here for SrF$_2$ by considering the dielectric relaxation parameters (R$_1$ relaxation mechanism) for crystals doped with trivalent ions of Ce, Eu and Gd, parameters for the anion Frenkel formation as well as for the migration of anion vacancy and the anion interstitial motion.
It is shown that the thermodynamic potential of the domain-like incommensurate (IC) phase of the K_2SeO_4 crystal should be supplemented with a term, taking into account the local, Lorentz electric field. The latter qualitatively changes the result of calculation of the dielectric susceptibility for this IC structure by Nattermann and Trimper, J. Phys. C: Solid State Phys. 14, 1603, (1981), and gives phase transition to the ferroelectric IC phase obtained by Aslanyan, Phys. Rev. B 70, 024102, (2004).
We perform first-principles calculations to explore electronic, thermodynamic, and dielectric properties of two-dimensional (2D) layered, alkaline-earth hydroxides Ca(OH)2 and Mg(OH)2. We calculate the lattice parameters, exfoliation energies, and phonon spectra of monolayers and also investigate the thermal properties of these monolayers such as Helmholtz free energy, heat capacity at constant volume, and entropy as a function of temperature. We employ Density Functional Perturbation Theory (DFPT) to calculate the in-plane and out-of-plane static dielectric constant of the bulk and monolayer …
The usual approach to the development of new nonlinear dielectric materials focuses on the search for materials in which the components possess an inherently large nonlinear dielectric response. In contrast, based on thermodynamics, we have presented a first-principles approach to obtain the electrostriction-induced effective third-order nonlinear susceptibility for the electrorheological (ER) fluids in which the components have inherent linear, rather than nonlinear, responses. In detail, this kind of nonlinear susceptibility is in general of about the same order of magnitude as the compressi…
Modeling ferroelectric materials from first principles is one of the successes of density-functional theory, and the driver of much development effort, requiring an accurate description of the electronic processes and the thermodynamic equilibrium that drive the spontaneous symmetry breaking and the emergence of macroscopic polarization. We demonstrate the development and application of an integrated machine learning model that describes on the same footing structural, energetic and functional properties of barium titanate ($\text{BaTiO}_3$), a prototypical ferroelectric. The model uses ab ini…
This paper verifies two laws for plastic flows of face-centered cubic crystals that deform at constant strain rates and fixed ambient temperatures. The first law relates steady-state flow stress to ambient temperature and strain rate. The second law requires an increase of configurational entropy towards a maximum reached in the steady state. The large scale least squares analysis is provided which allows the physics-based parameters of thermodynamic dislocation theory to be identified in accordance with these laws.
Results of low temperature dielectric measurements on the mixed (Ca_(1-x)Pb_(x))TiO_(3) system are presented to show that a dielectric anomaly appears for x \geq 0.10. The observed dielectric peak is shown to be due to a thermodynamic phase transition and not due to a relaxor or dipole glass type transition. Curie-Weiss fit to the dielectric constant gives negative Curie temperature which points towards an antiferroelectric transition. Arguments are advanced to propose that CaTiO3 may be an incipient antiferroelectric in which Pb^(2+) substitution stabilises the antiferroelectric phase.
The discovery of high-dielectric materials is crucial to increasing the efficiency of electronic devices and batteries. Here, we report three previously unexplored materials with very high dielectric constants (69 $<$ $ε$ $<$ 101) and large band gaps (2.9$<$ $E_{\text{g}}$(eV) $<$ 5.5) obtained by screening materials databases using statistical optimization algorithms aided by artificial neural networks (ANN). Two of these new dielectrics are mixed-anion compounds (Eu$_5$SiCl$_6$O$_4$ and HoClO), and are shown to be thermodynamically stable against common semiconductors via phase-diagram analy…
X-ray powder diffraction (XRD) along with differential thermal analysis (DTA) carried out on the as-quenched samples in the 3BaO-3TiO2-B2O3 system confirmed their amorphous and glassy nature, respectively. The dielectric constants in the 1 kHz-1 MHz frequency range were measured as a function of temperature (323-748 K). The dielectric constant and loss were found to be frequency independent in the 323-473 K temperature range. The dielectric behavior was consistent with the universal dielectric response (UDR). The temperature coefficient of dielectric constant was estimated using Havinga's form…
In this work we present the dielectric behavior of water with a novel flexible model that improved all three sites water models Different concentrations of the ionic liquid 1- butyl-3-methylimidazolium [bmim] bis(trifluoromethanesulfonyl)imide [Tf 2 N] with water was investigated. The study was performed by molecular dynamics simulations using three water models, being two non-polarizable 3-site SPC/E and SPC/e, and a novel flexible 3-site FAB/epsilon model. Systematic thermodynamics, dynamical and dielectric properties were investigated, such as density, diffusion coefficient, heat of vaporiz…
We have found a remarkable increase (up to 60 %) of the dielectric constant with the onset of magnetic order at 42 K in the metastable orthorhombic structures of YMnO3 and HoMnO3 that proves the existence of a strong magneto-dielectric coupling in the compounds. Magnetic, dielectric, and thermodynamic properties show distinct anomalies at the onset of the incommensurate magnetic order and thermal hysteresis effects are observed around the lock-in transition temperature at which the incommensurate magnetic order locks into a temperature independent wave vector. The orders of Mn3+ spins and Ho3+…
We present a thorough dielectric investigation of the hexagonal perovskites La1.2Sr2.7IrO7.33 and La1.2Sr2.7RuO7.33 in a broad frequency and temperature range, supplemented by additional infrared measurements. The occurrence of giant dielectric constants up to 10^5 is revealed to be due to electrode polarization. Aside of dc and ac conductivity contributions, we detect two intrinsic relaxation processes that can be ascribed to ionic hopping between different off-center positions. In both materials we find evidence for charge transport via hopping of localized charge carriers. In the infrared r…
Motivated by recent experiments on the finite temperature Mott transition in VO2 films, we propose a classical coarse-grained dielectric breakdown model where each degree of freedom represents a nanograin which transitions from insulator to metal with increasing temperature and voltage at random thresholds due to quenched disorder. We describe the properties of the resulting non-equilibrium metal-insulator transition and explain the universal characteristics of the resistance jump distribution. We predict that by tuning voltage, another critical point is approached, which separates a phase of …
