Structural phase transition,ionic conductivity,and dielectric investigations in K3H(SO4)2 single crystals

Optical observation, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) measurements have been carried out on K₃H(SO₄)₂ crystal in the temperature range between 25 and 300 °C. Domain structures of K₃H(SO₄)₂ were observed at room temperature which are the same as those observed in other member of A₃H(XO₄)₂ which show ferroelasticity. Two endothermic peaks of DSC were found at around 206 and 269 °C. In this temperature range, the result of TGA indicate the loss of weight. It supports that partial dehydration is most probable. The first peak can be accounted for the dehydration reaction on the surface of crystals, and the second peak corresponds to the melting of the sample crystal. The impedance measurements were performed as a function of both temperature and frequency. The electrical conductivity increases with increasing temperature and the sample crystal becomes a fast ionic conductor at the temperatures above 206 °C. The high conductivity of the crystal is caused by the increases of the defects due to the dehydration. The dielectric properties of the sample crystal were studied by the impedance spectroscopy.     

Electron paramagnetic resonance investigation of K3H(SO4)2 proton conductor doped with Cr ion

The proton arrangement around SO₄ units in K₃H(SO₄)₂ (KHS) was studied in detail by X-band CW EPR spectra of CrO₄³⁻ paramagnetic centre incorporated into KHS during the crystal growth process. The EPR data prove the theoretical model of coherent motion of protons and SO₄ units at the fast-proton conducting phase proposed by Ito and Kamimura.     

Studies of structure, thermal, and electrical properties for Cs 5 H 3 (SO 4 ) 4 crystal

Electrical conductivity, differential scanning calorimetry, and X-ray diffraction measurements were performed on a pentacesium trihydrogen tetrasulfate, Cs₅H₃(SO₄)₄, crystal. The transition entropy at a superionic phase transition and the activation energy of proton migrations in the superionic phase were determined to be 58.2 J K⁻¹ mol⁻¹ and 0.48 eV, respectively. The crystal structure of Cs₅H₃(SO₄)₄ at room temperature was refined. The electrical conduction in Cs₅H₃(SO₄)₄ was discussed with the refined structure.     

A nuclear magnetic resonance study of the phase transitions and electric quadrupole Raman processes of M5H3(SO4)4·H2O (M=Na, K, Rb, and Cs) single crystals

The spin–lattice relaxation times and spin–spin relaxation times for ¹H and M in M₅H₃(SO₄)₄·H₂O (M=Na, K, Rb, and Cs) single crystals grown using the slow-evaporation method were measured as functions of temperature. Two kinds of protons were identified in the M₅H₃(SO₄)₄·H₂O structure: acid protons and water protons. Our experimental results show that the acid and water protons in Cs₅H₃(SO₄)₄·H₂O are involved in phase transitions of this crystal, whereas neither type of proton is involved in the phase transitions of the other three crystal type (M₅H₃(SO₄)₄·H₂O; M=Na, K, and Rb). Moreover, the relaxation times for the M (=Na, K, and Rb) nuclei in these crystals were found to decrease with increasing temperature and can be described with (k=2). The T₁ results for M (=Na, K, and Rb) in M₅H₃(SO₄)₄·H₂O crystals can be explained in terms of a relaxation mechanism in which the lattice vibrations are coupled to the nuclear electric quadrupole moments.     

Effect of temperature and high pressure on Mn2+ EPR spectra in K3H(SO4)2 fast-proton conductor

The linewidth ΔH _pp and spin-Hamiltonian parameters under temperature and high hydrostatic pressure by X-band continuous wave electron paramagnetic resonance in the K₃H(SO₄)₂ crystal were studied. Spin-Hamiltonian parameters, direction cosines and coordination of Mn²⁺ ion were determined at room temperature. The pressure at 300?MPa leads to the change of hydrogen bond potential and the transition from double well to single well potential moves about 10?K towards a higher temperature.     

A study of molecular motion and Raman processes in K3H(SO4)2 and KHSO4 single crystals by observation of H and K spin-lattice relaxation

The spin-lattice relaxation rates for ¹H and ³⁹K nuclei in K₃H(SO₄)₂ and KHSO₄ single crystals, which are potential candidate materials for use in fuel cells, were determined as a function of temperature. The spin-lattice relaxation recovery of ¹H can be represented for both crystals with a single exponential function, but cannot be represented by the Bloembergen-Purcell-Pound (BPP) function, so is not related to HSO₄ motion. The recovery traces of ³⁹K, which predominantly undergoes quadrupole relaxation, can be represented by a linear combination of two exponential functions. The temperature dependences of the relaxation rates for ³⁹K can be described with a simple power law T₁⁻¹=αT². The spin-lattice relaxation rates for the ³⁹K nucleus in K₃H(SO₄)₂ and KHSO₄ crystals are in accordance with a Raman process dominated by a phonon mechanism.     

Low-temperature phase transitions and dynamics of ammonium in (NH4)3H(SO4)2 and [(NH4)1−x Rbx]3H(SO4)2 crystals

The (NH₄)₃H(SO₄)₂ and [(NH₄)_0.82Rb_0.18]₃H(SO₄)₂ crystals are investigated by dielectric spectroscopy, inelastic incoherent neutron scattering (IINS), and neutron powder diffraction. A comparative analysis of the data obtained is given. It is shown that the phase transitions II ? III, III ? IV, IV ? V, and V ? VII in the (NH₄)₃H(SO₄)₂ crystal are accompanied by changes in the orientation ordering of the NH ₄ ⁺ ions. In the [(NH₄)_0.82Rb_0.18]₃H(SO₄)₂ crystal, these phase transitions are completely suppressed and the long-range order inherent in the II phase is retained over the entire temperature range covered (6–300 K). It is revealed that this crystal at the temperature T _g≈70 K undergoes a transition to the dipole glass phase, which is attended by “freezing” the orientation disordering of the ammonium ions.     

Recent results on K ? multinucleon absorption by FINUDA

K₂Fe₃(OH)₂(SO₄)₃(H₂O)₂ was prepared by hydrothermal synthesis. The crystal structure is the isomorphous phase of K₂Co₃(OH)₂(SO₄)₃(H₂O)₂. M?ssbauer spectra of K₂Fe₃(OH)₂(SO₄)₃(H₂O)₂ were measured at low temperatures between room temperature and 14?K, and the hyperfine interactions were analyzed. The Neel temperature is 39?K. Two paramagnetic Fe^2?+? species were observed in the M?ssbauer spectrum at room temperature, and M?ssbauer spectra measured below 38?K were decomposed into four magnetic subspectra. From the temperature dependence, it is found that the local electron density at each site is largely deviating at low temperatures, which may induce the giant coercivity.     

Quantum Effect on the Energy Levels of Eu2+ Doped K2Ca2(SO4)3 Nanoparticles

Quantum confinement effect on the energy levels of Eu²⁺ doped K₂Ca₂(SO₄)₃ nanoparticles has been observed. The broad photoluminescence (PL) emission band of Eu²⁺ doped K₂Ca₂(SO₄)₃ microcrystalline sample observed at ～436 nm is found to split into two narrow well resolved bands, located at 422 and 445 nm in the nanostructure form of this material. This has been attributed to the reduction in the crystal field strength of the nanomaterials, which results in widening the energy band gap and splitting the broad 4f⁶5d energy level of Eu²⁺. Energy band gap values of the micro and nanocrystalline K₂Ca₂(SO₄)₃ samples were also determined by measuring the UV–visible absorption spectra. These values are 3.34 and 3.44 eV for the micro and nanocrystalline samples, respectively. These remarkable results suggest that activators having wide emission bands might be subjected to weak crystal strength via nanostructure materials to modify their electronic transitions. This might prove a powerful technique for producing new-advanced materials for use in the fields of solid state lasers and optoelectronic devises.     

Raman study of cation effect on sulfate vibration modes in solid state and in aqueous solutions

Raman spectra of potassium, sodium, and ammonium sulfates (K₂SO₄, Na₂SO₄, and (NH₄)₂SO₄) are reported and analyzed. These sulfates have been investigated under two states: solid (anhydrous and hydrated) salts and aqueous solutions. The effects of monovalent ions (K⁺, Na⁺, and NH₄⁺) and hydration on the position of Raman lines assigned to internal vibrations of sulfate anion SO₄²⁻ are discussed. In solid salts, the line position of each Raman peak is shown to decrease with increasing radius of the cation. The main ν₁ mode of sulfate molecule is particularly affected. It is emphasized that this sensitivity in solid sulfates vanishes in aqueous solutions. As a consequence, this mode can be probed by Raman spectroscopy as the main signature of SO₄²⁻ to determine its concentration within a single calibration. Copyright © 2013 John Wiley & Sons, Ltd.     

Dielectric and AC ionic conductivity investigations in K3H(SeO4)2 single crystal

Optical observation under the polarizing microscope and DSC measurements on K₃H(SeO₄)₂ single crystal have been carried out in the temperature range 25-200 °C. It reveals a high-temperature structural phase transition at around 110 °C. The crystal system transformed from monoclinic to trigonal. Electrical impedance measurements of K₃H(SeO₄)₂ were performed as a function of both temperature and frequency. The electrical conduction and dielectric relaxation have been studied. The temperature dependence of electrical conductivity indicates that the sample crystal became a fast ionic conductor in the high-temperature phase. The frequency dependence of conductivity follows the Jonscher's universal dynamic law with the relation σ(ω)=σ(0)+Aωⁿ, where ω is the frequency of the AC field, and n is the exponent. The obtained n values decrease from 1.2 to 0.1 from the room temperature phase to fast ionic phase. The high ionic conductivity in the high-temperature phase is explained by the dynamical disordering of protons between the neighboring SeO₄ groups, which provide more vacant sites in the crystal.     

Structural, vibrational and dielectric properties of new potassium hydrogen sulfate arsenate: K4(SO4)(HSO4)2(H3AsO4)

A new compound, K₄(SO₄)(HSO₄)₂(H₃AsO₄) was synthesized from water solution of KHSO₄/K₃H(SO₄)₂/H₃AsO₄. This compound crystallizes in the triclinic system with space group P1¯ and cell parameters: a=8.9076(2) Å, b=10.1258(2) Å, c=10.6785(3) Å; α=72.5250(14)°, β=66.3990(13)°, γ=65.5159(13)°, V=792.74(3) Å³, Z=2 and ρ_cal=2.466 g cm⁻³. The refinement of 3760 observed reflections (I>2σ(I)) leads to R₁=0.0394 and wR₂=0.0755. The structure is characterized by SO₄²⁻, HSO₄⁻ and H₃AsO₄ tetrahedra connected by hydrogen bridge to form two types of dimer (H(16)S(3)O₄⁻?S(1)O₄²⁻ and H(12)S(2)O₄⁻?H₃AsO₄). These dimers are interconnected along the [1¯ 1 0] direction by the hydrogen bonds O(3)-H(3)?O(6). They are also linked by the hydrogen bridge assured by the hydrogen atoms H(2), H(3) and H(4) of the H₃AsO₄ group to build the chain S(1)O₄?H₃AsO₄ which are parallel to the “a” direction. The potassium cations are coordinated by eight oxygen atoms with K-O distance ranging from 2.678(2) to 3.354(2) Å.Crystals of K₄(SO₄)(HSO₄)₂(H₃AsO₄) undergo one endothermic peak at 436 K. This transition detected by differential scanning calorimetry (DSC) is also analyzed by dielectric and conductivity measurements using the impedance spectroscopy techniques. The obtained results show that this transition is protonic by nature.     

First principles investigation of hydrogen isotope effects in [XSO4–H–SO4X]− (X = H,K) complexes

Hydrogen isotope effects on geometries, total energies, nuclear and electronic wave functions of the [HO₃SO–H–OSO₃H]^? and [KO₃SO–H–OSO₃K]^? complexes are investigated with the NEO/HF method. This method determines both electronic and nuclear wave function simultaneously. A discussion of the isotope effects is provided and used to explain the hydrogen isotope effects on the phase transition temperatures in hydrogen bonded ferroelectric materials, K₃H(SO₄)₂ and K₃D(SO₄)₂.     

Proton Dynamics in Letovicite, (NH4)3H(SO4)2: A H and N NMR Spectroscopic Study

The improper ferroelastic phase letovicite (NH₄)₃H(SO₄)₂ has been studied by ¹H MAS NMR as well as by static ¹⁴N NMR experiments in the temperature range of 296–425 K. The ¹H MAS NMR resonance from ammonium protons can be well distinguished from that of acidic protons. A third resonance appears just below the phase transition temperature which is due to the acidic protons in the paraelastic phase. The lowering of the second moment M₂ for the ammonium protons takes place in the same temperature range as the formation of domain boundaries, while the signals of the acidic protons suffer a line narrowing in the area of T_c. The static ¹⁴N NMR spectra confirm the temperature of the motional changes of the ammonium tetrahedra. Two-dimensional ¹H NOESY spectra indicate a chemical exchange between ammonium protons and the acidic protons of the paraphase.     

High pressure behaviour of KHSO4 studied by electrical impedance spectroscopy

Measurements of the electrical conductivity were performed in KHSO₄ at pressures between 0.5 and 2.5 GPa and in the temperature range 120-350 °C by the use of the impedance spectroscopy. The temperatures of the α-β phase transition (T_Tr) and of the melting (T_m), determined from the Arrhenius plots ln(σT) vs. 1/T, increase with pressure up to 1.5 GPa having dT/dP∼+45 K/GPa. Above the pressure 1.5 GPa, the pressure dependencies of T_Tr and T_m are negative dT/dP∼−45 K/GPa. At pressures above 0.5 GPa, the reversible decomposition of KHSO₄ into K₃H(SO₄)₂+H₂SO₄ (and probably into K₅H₃(SO₄)₄+H₂SO₄) affects the electrical conductivity of KHSO₄, with the typical values of the protonic electrical conductivity, c. 10⁻¹ S/cm at 2.5 GPa.     

Low-frequency vibrational spectra of crystals of tutton salts

IR absorption spectra and polarized Raman spectra of crystals of Tutton salts K₂M(SO₄)₂6H₂O and (NH₄)₂M(SO₄)₂·6H₂O, where M=Co, Ni, Zn, have been obtained by experiment at 93 K and at room temperature. The frequencies and forms of normal modes of the [Zn(H₂O)₆]²⁺ octahedral complex have been calculated. The observed lines are assigned to the internal modes of the [M(H₂O)₆]²⁺ complex and external modes of the crystal lattice in accordance with the results of the calculations and factor-group analysis. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 4, pp. 445–449, July–August, 2000.     

Optical Properties of [(CH3)2NH2]5Cd3Cl11 Crystals in the Region of their Phase Transitions

A sequence of phase transitions in the [(CH₃)₂NH₂]₅Cd₃Cl₁₁ (DMACC) crystal has been verified based on the study of temperature dependences of the optical birefringence and the data of piezooptical investigations. Absorption spectra in the visible and near-UV regions and IR reflection spectra in the 200–2000-cm^–1 region have been obtained. Phase transitions at temperatures of 179.5, 151, and 120 K have been detected. For all the phases of the DMACC crystal, the optical absorption edge obeys Urbach's empirical rule. It is shown that the phonons corresponding to the internal vibrations of the (Cd₃Cl₁₁)^5– polyhedron participate in the edge formation.     

Laser Raman spectra of mixed crystals of [(NH4)1−x Kx]2 SO4

The Raman spectra of mixed crystals of [(NH₄)_1?x K _x ]₂ SO₄ in the region 50–3400 cm^?1 at 293 K and below 223 K have been reported. At room temperature 293 K, as the concentration of K⁺ ion increases in the crystal up to 50%, the frequencies of the totally symmetric vibrations of SO ₄ ^2? and NH ₄ ⁺ ions increase and thereafter the frequency of SO ₄ ^2? vibration decreases and attains the value in K₂SO₄. This change in frequency up to 50% of potassium concentration is due to the breaking of hydrogen bonds of the type N-H...O. The behaviour of Raman intensities of A _g (v ₁) mode of SO ₄ ^2? for various concentrations (x=0, 0·03, 0·11, 0·5, 0·85) suggest that the phase transition changes from first order type to one of second order. The phase transition in mixed crystals of [(NH₄)_1?x K _x ]₂ SO₄ can be a cooperative phenomenon arising from a coupling between (NH₄)⁺ ions through hydrogen bonds with the distorted SO ₄ ^2? ions in the low temperature phase.     

Analysis of the ferroelastic domains and phase transition in the K2SO4 crystal

Abstract

The domain structures of the β-K₂SO₄ crystal were analyzed by group theory. We obtained the permissible kinds of domain association and domain walls from the results of the group theory. It is suggested from the analysis that the (110) and (130) planes are W_mb walls. The value of the spontaneous strain of K₂SO₄ wast = 6.32 × 10^?3 at room temperature and also its temperature dependence was observed.     

Conductivity and dielectric relaxation phenomena in (NH4)2SO4 single crystal

AC impedance measurements have been carried out on (NH₄)₂SO₄ single crystals for the temperatures from 300 to 473 K and frequency range between 100 Hz and 4 MHz. The results reveal two distinct relaxation processes in the sample crystal. One is the dipolar relaxation with a peak at frequency slightly higher than 4 × 10⁶ Hz. The other is the charge carrier relaxation at lower frequencies. The frequency dependence of conductivity is described by the relation σ(ω) = Bωⁿ, and n = 1.32 is obtained at temperatures below 413 K. This value drops to 0.2 and then decreases slightly with increasing temperature. The dipolar response of the (NH₄)₂SO₄ single crystal under an ac field is attributed to the reorientation of dipoles. The contribution of charge carriers is increasing substantially with increasing temperature at temperatures above 413 K. The temperature variation of conductivity relaxation peaks follows the Arrhenius relation. The obtained activation energy for migration of the mobile ions for (NH₄)₂SO₄ single crystal was 1.24 eV in the temperature range between 433 and 468 K in this intrinsic region. It is proposed that the NH₄⁺ in the sample crystal has the contribution to the electrical conduction.