Two phonon density of states of partially disordered crystal NH4I

Two phonon density of states of NH₄ have been computed with the help of deformation dipole model at room temperature. The results have been compared with the available experimental Raman Spectrum and peak position. It has been shown that in addition to single phonon process which is dominant, the two-phonon density of states also contribute to the Raman Intensity in a partially disordered crystal.     

Mode-Grüneisen parameters in disordered molecular crystals: Raman spectra of NH4Br and NH4I under hydrostatic pressure

The Raman spectrum of NH₄I has been measured under hydrostatic pressure. The high pressure phase of NH₄I was identified with the disordered CsCl-type phase by comparing the spectrum with that of NH₄ Br. The mode-Grünesen parameters of NH₄Br and NH₄I were determined from the frequency shift of phonon bands under hydrostatic pressure. These values were compared with the thermodynamic value and that obtained from the Slater relation. Contributions to the thermodynamic Grüneisen constant are discussed from free energy terms of NH⁺₄-orientation and -interactions with lattice modes.     

The Raman spectra of NH4I at high pressures. The existence of a new phase in the ammonium halides

The Raman spectra of NH₄I and ND₄I show significant changes at higher pressures which can only be interpreted in terms of the existence of a new phase. This is not an intermediate phase occurring between phases II and IV, but is observed upon further compression of the ferro-ordered phase IV. Preliminary measurements show that the same phase transition occurs in NH₄Br and NH₄Cl, but at significantly higher pressures than the one in NH₄I.     

Static,anharmonic and phonon properties of ND4I

A detailed investigation of the phonon dispersion and static and anharmonic properties has been carried out for ND₄I using an extended three-body force shell model (ETSM) developed by Singh and Chandra. The ETSM results for phonon dispersion show better agreement with the experimental data than those obtained from the deformation dipole and rigid shell models. Calculated values have also been obtained for some other properties.     

Two-phase region in the lambda transition of NH4Br and ND4Br

The specific volumes of NH₄Br and ND₄Br were measured with a precision dilatometer, based on hydrostatic weighing, between 160° and 300°K to exanine the existence of a two-phase region in the lambda transition. Probably NH₄Cl and ND₄Cl have analogous two-phase regions.     

14N NMR in NH4I and NH4Br

¹⁴N magnetic resonance data show that the α → β transition in NH₄I is connected with a discontinuous change in the ¹⁴N chemical shift, Δδ = 20.5 ppm, whereas the order-disorder type β(O_h) → γ(D_4h) transition is accompanied by a small quadropole splitting of the ¹⁴N spectrum. A quadrupole splitting of the ¹⁴N line was as well found in the tetragonal “antiferromagnetically” ordered γ-phase of NH₄Br, but not in the “ferromagnetically” ordered δ(T_d) phase of NH₄Cl.     

Structural and thermal studies of PVA:NH4I

Proton-conducting polymer electrolytes based on poly vinyl alcohol (PVA; 88% hydrolyzed) and ammonium iodide (NH₄I) has been prepared by solution casting method with different molar ratios of polymer and salt using DMSO as solvent. DMSO has been chosen as a solvent due its high dielectric constant and also its plasticizing nature. The ionic conductivity has been found to increase with increasing salt concentration up to 25 mol% beyond which the conductivity decreases and the highest ambient temperature conductivity has been found to be 2.5×10⁻³ S cm⁻¹. The conductivity enhancement with addition of NH₄I has been well correlated with the increase in amorphous nature of the films confirmed from XRD and differential scanning calorimetry (DSC) analyses. The temperature-dependent conductivity follows the Arrhenius relation. The polymer-proton interactions have been analyzed by FTIR spectroscopy.     

Theory of Raman and FIR spectra induced by orientational disorder in NH4Cl and NH4I

We calculate the Raman scattering induced by the disorder of molecular orientations in the β phase of NH₄Cl and NH₄I by a shell model for the Raman polarizability. Comparison of the calculations with the experiments yields information about the interaction potential between halide shells and neighbouring H-atoms and leads to an assignment of the disorder induced bands. We also investigate the possibility of disorder induced FIR spectra. The selection rules and possible microscopic mechanisms are discussed.     

Phase situation in ferroelectric NH4HSeO4 crystals with various degrees of deuteration

NH₄HSeO₄ crystals of varying deuterium content have been studied. The high-temperature phase transition at 408 K is observed both for crystals of symmetry I2 grown from the solutions containing 0–40% D and those of symmetry P2₁2₁2₁ i.e. grown solutions containing above 50% D. This phase transition practically does not depend on %D. For the crystals of symmetry P2₁2₁2₁ an additional dielectric anomaly at 338 K (only slightly dependent on %D) has been found which most probably should be assigned to the P2₁2₁2₁-I2 transition. The results obtained and our earlier data available so far enabled to construct more detailed phase diagram for NH₄HSeO₄ with %D as a parameter.     

Raman study of NH4NO3 and ND4NO3—250–420K

Raman spectra of NH₄NO₃, and ND₄NO₃, were studied from 250 to 420K. The results show that there are four phases separated by first order transitions. No evidence of the previously reported phase II' was observed.The present results combined with the results of other experiments present the following picture of the state of order of the molecules.In phase I, the highest temperature phase, the NH₄⁺ groups are in a free rotation and the nitrate groups are likely in random reorientation among 12-equivalent positions. In phase II, the NH₄⁺ groups are likely in rapid random reorientation under the local force field of S₄ symmetry. The nitrate groups are in hindered rotation but are disordered with one of the O-N bonds directed in one sense or the other along the c-axis. In phase III, the absence of the librational mode indicates that the NH₄⁺ groups are in nearly free rotation but the rotational motion is restricted by the local force field of C₃ symmetry. The nitrate groups are probably ordered as suggested by the well polarized character of the modes associated with the nitrate groups. In phase IV, the nitrate groups are ordered with their molecular planes perpendicular to the b-axis. The NH₄⁺ groups are in orientational disorder but may undergo bindered rotations. An optical mode was observed to couple to an anomalous mode which is believed to be a zone edge acoustical mode.     

Heat capacity and phase transitions in NH4LiSO4, Csx(NH4)1?xLiSO4, and RbLiSO4

The heat capacity of NH₄LiSO₄, RbLiSO₄ and Cs_x(NH₄)_1−x LiSO₄ crystals and its behavior over a broad temperature range including the phase transition regions were studied. The entropy changes corresponding to structural transformations in these crystals were found not to be characteristic of straightforward ordering of structural blocks. The results obtained are discussed in terms of phenomenological theory and model concepts. __________ Translated from Fizika Tverdogo Tela, Vol. 47, No. 4, 2005, pp. 696–704. Original Russian Text Copyright ? 2005 by Flerov, Kartashev, Grankina.     

Low temperature electrical conductivity,dielectric constant,and phase transitions in (NH4)2SO4 and (ND4)2SO4

Careful axiswise measurements of d.c. conductivity and dielectric constants of (NH₄)₂SO₄ from 50 to - 196°C establish two distinct phase transitions, instead of one, at temperatures -49.5 and -58°C which remain unchanged in (ND₄)₂SO₄. Explanation based on successive distortions of non-equivalent (NH₄)⁺ is offered. Low temperature transport process in the crystal also is discussed.     

Anomalous thermoelastic behaviour of orientationally disordered (NH4I)x(KI)1−x mixed crystals

We have incorporated the translational rotational (TR) coupling effects in the framework of three body force shell model (TSM) to develop an extended TSM (ETSM). This ETSM has been applied to reveal the second order elastic constants (C₁₁, C₁₂ and C₄₄) in the dilute regimes 0≤x≤0.50. Our theoretical results have reproduced well the observed variations of C₁₁ (x=0.14, 0.43) and C₁₂ (x=0.14, 0.43) with temperature. The anomalous elastic behaviour observed in C₄₄ below 150 K for x=0.43 has been predicted well by ETSM results in the orientationally disordered (NH₄I)_x(KI)_1−x mixed crystals. Our results for C₁₂ are in good agreement with the experimental data available for x=0.14 and 0.43. Besides, the third and fourth order elastic constants and the results on cohesive and thermophysical properties are also discussed.     

Effective ionic charges in CdGa2Se4 and CdGa2S4

Available experimental data (Raman and Infrared) on the optic phonon spectra in defect chalcopyrite crystals CdGa₂Se₄ and CdGa₂S₄ are used to determine the dynamical ionic effective charges. The results are compared with those found in other ternary compounds as spinels and chalcopyrites. An emperical correlation between the normalized Szigeti charges and the optical dielectric constant is discussed.     

High-resolution diode laser spectra of the ν4 mode of 12CF3I and 13CF3I

High-resolution spectra of the ν₄ mode of ¹²CF₃I and ¹³CF₃I have been recorded using diode laser spectroscopic techniques. The sample was cooled to 163 ± 10 K to suppress the hot bands. Natural CF₃I containing 98.9% ¹²CF₃I and 1.1% ¹³CF₃I was used for recording the spectra. About 1200 lines in the P and R branches of each isotopic molecule have been assigned and used in the least-squares fit. The pseudoparallel structure of the bands has been understood and accurate values of rotational constants have been obtained.     

Growth and comparison of physicochemical properties of pure,Ca and Sr doped NH4Sb3F10 single crystals for electro optic applications

Single crystals of pure, Ca²⁺ and Sr²⁺ doped NH₄Sb₃F₁₀ are grown by slow evaporation technique. The effect of dopants on the growth and physicochemical properties also have been investigated and reported for the first time. The grown crystals are characterized with the aid of single crystal X-ray diffractometry to confirm the crystal structure. EDAX studies are done to confirm the presence of dopants in the crystal lattice. The vibrational frequencies of various group ligands in the crystals have been derived from the Fourier transform infrared (FT-IR) spectrum. From the optical absorption spectrum the band gap energy was calculated and it was found to be 5.76, 6.29 and 6.35 eV for pure, Ca²⁺ and Sr²⁺ doped NH₄Sb₃F₁₀ crystals respectively. Thermal stability of the sample has been analysed using TG-DTA analysis. The activation energy of pure, Ca²⁺ and Sr²⁺ doped NH₄Sb₃F₁₀ crystals were calculated from the dc conductivity measurements and it is found to be 0.2728, 0.2816 and 0.3622 eV Experimental results shows improved physicochemical properties when the dopant is added to the pure material.     

A new interpretation of the critical behavior in NH4Cl and ND4Cl

It is proposed that the first order transition of NH₄Cl and ND₄Cl is not located near a tricritical point but near a critical point of type 4. Good agreement between the measured and calculated values of the critical exponent β and α′ is obtained.     

Incommensurability and metastability problems in NH4HSeO4 and ND4DSeO4: A reinvestigation of phase diagrams

Abstract

X-ray and neutron diffraction results on NH₄HSeO₄ and ND₄DSeO₄ are reported. Direct evidence of an incommensurate phase sandwiched between the monoclinic high-temperature phase (space group B2) and the low-temperature ferroelectric lock-in phase k = ? (space group P1) has been obtained in NH₄HSeO₄. The phase situation is more complicated in ND₄DSeO₄, where an incommensurate phase is found sandwiched between the B2 phase and a lock-in phase k = ¼ and where a phase in which several modulations coexist has been discovered in between the two lock-in phases k = ¼ and k = ?. The non-equilibrium processes, also present in ND₄DSeO₄, have been identified. All these results have clarified the situation about the phase diagram.     

The 5νNH and 5νND vibrational bands of partially deuterated ammonia species

Absorption spectra of gaseous samples containing NH₂D and NHD₂ have been measured in the 11 580-11 880 and 15 280-15 610 cm⁻¹ regions, corresponding to the 5ν_ND and 5ν_NH vibrational bands, respectively. Photoacoustic spectroscopy has been utilized for the measurement. The molecular constants of NH₂D in the 5ν_ND state and NHD₂ in the 5ν_NH state have been determined from the analysis of the obtained absorption spectrum. From the comparison of the constants with those of the vibrational ground states, structural changes caused by the stretching excitations have been elucidated. The HND bond angles are decreased by these excitations. The dependence of the molecular constants on the stretching quantum number has also been derived by simple Birge-Sponer and Dunham analyses.     

On the deuteron magnetic resonance in single crystals of ND4Cl and ND4Br

The deuteron quadrupole coupling constants in ND₄Cl and ND₄Br have been measured. The results are 179.9±2.0 and 180.0±2.0 kHz, respectively. From the temperature dependence of the line width in ND₄Cl for the d. c. magnetic field along [100] the hindered rotation potential barrier of the ND₄ ⁺-ion was found to be 5.1 kcal/mole. In crystals containing moisture a narrow line component was observed, which is probably due to the formation of an eutectic solution.