Longitudinal and transverse properties of KD2PO4 — A Monte Carlo study

The three dimensional pseudo-spin model of KD₂PO₄ (DKDP) has been investigated by using the Monte Carlo method. The model is found to exhibit simultaneous longitudinal ferroelectric and transverse antiferro-electric behaviour, and the results are shown to be in good quantitative agreement with experiment.     

Neutron inelastic scattering from mixed salts [(NH4)xK1−x]2SO4

Neutron inelastic scattering measurements have been performed on [(NH₄)_xK_1?x]₂SO₄. It is shown that NH₄⁺ preferentially occupies one of the two available inequivalent sites at smaller concentrations. NH₄⁺ at the other site seems to be necessary for the occurance of ferroelectricity in these compounds.     

First-order phase transition to strongly anisotropic ferromagnetism in Tl2Fe6Te6

The magnetic susceptibility, magnetization, specific heat and electrical resistivity were measured on the new material Tl₂Fe₆Te₆. All the data show a very sharp anomaly revealing a phase transition to ferromagnetism at T_c≈220 K. The presence in the structure of one-dimensional metallic clusters $\text{¦Fe}{}_3\text{¦}{}^1{}_{\mathrm{\infty }}$ is evidenced by a very strong magnetic anisotropy in the ferromagnetic state, showing an interesting intermediate situation between a pure linear chain and 3-dimensional iron. Furthermore, the unusual sharpness of the transition leads us to anticipate a first-order phase transformation, but the lack of detectable thermal hysteresis was surprising. The molecular field model proposed by Bean and Rodbell in order to account for the similar behavior of MnAs gives a close representation of our magnetic data. Thus, a pronounced dependence of the exchange interaction upon interatomic spacing may well be the dominant mechanism leading to the observed phenomena.     

The crystal structures of the ion conductors (NH+4)Zr2(PO4)3and (H3O+)Zr2(PO4)3

The crystal structures of (NH⁺₄)Zr₂(PO₄)₃ and (H₃O⁺)Zr₂(PO₄)₃ have been determined from neutron time-of-flight powder diffraction data obtained at 15 K. Both compounds are rhombohedral, $\text{R}\text{3}\text{c}$, with cell parameters a=8.7088(1) and c=24.2197(4) Å for the ammonium compound and a=8.7528(2), c=23.6833(11) Å for the hydronium compound. In both cases the ions are completely localized in the type I cavities and hydrogen bonded to lattice oxygens. The measured unit cell parameters are relatively large for this class of compounds but the entrance ways into the cavities are still too small to allow for unrestricted movement of the ions. Thus the low conductivity of the hydronium ion is related to this and other structural features.     

The ν2, 2ν2, 3ν2, ν4, and ν2 + ν4 bands of 15NH3

The ir absorption of gaseous ¹⁵NH₃ between 510 and 3040 cm^?1 was recorded with a resolution of 0.06 cm^?1. The ν₂, 2ν₂, 3ν₂, ν₄, and ν₂ + ν₄ bands were measured and analyzed on the basis of the vibration-rotation Hamiltonian developed by V. ?pirko, J. M. R. Stone, and D. Papou?ek (J. Mol. Spectrosc.60, 159–178 (1976)). A set of effective molecular parameters for the ν₂ = 1, 2, 3 states was derived, which reproduced the transition frequencies within the accuracy of the experimental measurements. For ν₄ and ν₂ + ν₄ bands the standard deviation of the calculated spectrum is about four times larger than the measurements accuracy: a similar result was found for ν₄ in ¹⁴NH₃ by ?. Urban et al. (J. Mol. Spectrosc.79, 455–495 (1980)). This result suggests that the present treatment takes into account only the most significant part of the rovibration interaction in the doubly degenerate vibrational states of ammonia.     

Ultrasonic propagation near the ferroelectric phase transition temperature in RbH2PO4

Ferroelectric phase transition in RbH₂PO₄ is studied by the propagation of longitudinal ultrasonic waves along the polar axis. The velocity data are analyzed to obtain the temperature dependence of the soft mode frequency in the ferroelectric phase. Unlike KH₂PO₄ and KD₂PO₄, the attenuation in RbH₂PO₄ does not exhibit a relaxation type behaviour.     

High temperature Raman scattering and phase transition in EuAlO3

Polarized Raman spectra of EuAlO₃ have been obtained at various temperatures from 77–1500 K. Three phonon modes are observed to soften in frequency with increasing temperature. Discontinuity in the frequency temperature dependence appears at 1420 K. This result is consistent with a first order phase transition. Analysis of the Raman data shows evidence of a coupling between the soft mode of Bg(XY) symmetry and one mode of same symmetry.     

Molecular constants for the interacting upper states of the ν1, ν3, 2ν2, ν2 + ν4, and 2ν4 bands in 12CH4

In a previous paper (J.-E. Lolck and A. G. Robiette, J. Mol. Spectrosc.88, 14 (1981)) a theoretical model for the interacting upper states of the ν₁, ν₃, 2ν₂, ν₂ + ν₄, and 2ν₄ bands in methane was described. The present paper summarizes the results obtained, using this model, in a comprehensive analysis of the five bands of ¹²CH₄ through J′ = 12. Values of 80 molecular constants, of which 17 correspond to vibrationally off-diagonal operators, are reported. In addition the computed energy levels of the v₃ = 1 state are compared to the experimental ones and to the result of the previous isolated band approach.     

The ν2 + ν4 and 2ν2 isotropic Raman bands of 12CH4

The purely isotropic Raman spectrum of the ν₁ band, the ν₂ + ν₄ band (enhanced through interaction with ν₁), and the 2ν₂ band of ¹²CH₄ was obtained with a spectral resolution of 0.30–0.35 cm^?1 from exposures with different orientations of the linearly polarized exciting light. The ν₂ + ν₄ and 2ν₂ bands show partially resolved rotational structure. The spectra are interpreted in terms of a model which takes explicitly into account vibrational and rovibrational interactions with other vibrational states, using molecular constants determined primarily from infrared spectra. The computed contours are in excellent agreement with the experimental ones and the observed and calculated peak wavenumbers agree within one tenth of the spectral resolution limit, except for a small region near the ν₁ band. The good overall agreement represents an independent check on the overall correctness of the previously reported molecular constants. A detailed discussion is given of the contributions to the intensities of individual transitions from the three transition moment matrix elements, which in an isolated-band model are the intensity parameters of the ν₁, 2ν₄, and 2ν₂ isotropic bands, respectively.     

A theoretical model for the interacting upper states of the ν1, ν3, 2ν2, ν2 + ν4, and 2ν4 bands in methane

The effective vibration-rotation Hamiltonians complete to fourth order in the Amat-Nielsen scheme for the upper states of the ν₁, ν₃, 2ν₂, ν₂ + ν₄, and 2ν₄ bands in methane are reviewed, and the major vibration-rotation interactions (H₃₀, $\text{H}\text{?}{}_{40}$, $\text{H}\text{?}{}_{21}$, $\text{H}{}_{31}$, $\text{H}\text{?}{}_{22}$) connecting the different vibrational states are discussed. Explicit matrix elements in a basis of harmonic oscillator-symmetric rotor basis functions are given for the purely vibrational terms and for the vibration-rotation interactions. Expressions for spectral intensities of infrared and Raman spectra are presented, and the selection rules and transition moment matrix elements are stated. A computer program is described which, incorporating all these features, can be used for prediction of infrared and Raman spectra and for determination of molecular constants from observed spectra by a least-squares routine. As an example the program is applied to the 2ν₄ isotropic Raman spectrum of ¹²CH₄, leading to a very good agreement between the experimental and calculated spectra.     

N2-broadening coefficients in the ν2 and ν4 bands of PH3 at low temperature

N₂-broadening coefficients have been measured for 41 transitions of PH₃ at −100 °C in the ^QR branch of the ν₂ band and the ^PP, ^RP, and ^SP branches of the ν₄ band, using a tunable diode-laser spectrometer. The recorded lines with J values ranging from 1 to 13 and K from 0 to 10 are located between 1026 and 1093 cm⁻¹. The collisional widths are determined by fitting each spectral line with a Voigt profile, a Rautian profile, and a speed-dependent Rautian profile. The latter models provide larger broadening coefficients than the Voigt model. These coefficients have also been calculated on the basis of a semiclassical model of interacting linear molecules by considering an atom-atom Lennard-Jones potential in addition to the electrostatic contributions. By comparing broadening coefficients at room and low temperatures, the temperature dependence of these broadenings has been determined both experimentally and theoretically.     

The antiferroelectric phase transition in TlH2PO4 and TlD2PO4

It is shown by X-ray diffraction measurements that the transitions at 230 K in TlH₂PO₄ and at ≈ 350 K in TlD₂PO₄ are structurally equivalent. In both cases, on cooling through the transition, new reflections appear at points ($\text{h +}\text{1}\text{2}$, $\text{k +}\text{1}\text{2}$, l) referred to the primitive monoclinic unit cell of the high-temperature phase. In TlH₂PO₄ some distinct but broadened scattering remains at the ($\text{h +}\text{1}\text{2}$, $\text{k +}\text{1}\text{2}$, l) points up to 10 K, or more, above the transition temperature.     

Pressure-induced phase transition in defect Chalcopyrites HgAl2Se4 and CdAl2S4

Results of angle dispersive X-ray diffraction (ADXRD) measurements on the defect chalcopyrites (DCP), HgAl₂Se₄ and CdAl₂S₄ up to 22.2 and 34 GPa, respectively, are reported. The ambient tetragonal phase is retained in HgAl₂Se₄ and CdAl₂S₄ up to 13 and 9 GPa respectively. The values of the bulk modulus estimated from the Equation of State is 66(1.5) and 44.6(1) GPa for HgAl₂Se₄ and CdAl₂S₄ in the chalcopyrite phase. At higher pressure a disordered rock-salt structure and on pressure release a disordered zinc blende structure with broad X-ray diffraction lines are observed as is the case for several defect chalcopyrites.     

Hydrogen line broadening in the ν2 and ν4 bands of phosphine at low temperature

Using a tunable diode-laser spectrometer, we have measured H₂-broadening coefficients of PH₃ at low temperature (173.2 K) for 27 lines in the ^QR branch of the ν₂ band and in the ^PP and ^RP branches of the ν₄ band. The recorded lines with J values ranging from 2 to 11 and K from 0 to 9 are located between 1016 and 1093 cm⁻¹. The collisional widths are determined by fitting each spectral line with a Voigt profile and a speed-dependent Rautian profile which provides slightly larger broadening coefficients than the Voigt model. These coefficients have also been calculated on the basis of a semiclassical model of interacting linear molecules by considering an atom-atom Lennard-Jones potential in addition to the weak electrostatic contributions. Except for three ^QR(J,K) lines, where K = J, the calculated broadening coefficients are in good agreement with the experimental data. By comparing the results obtained at room and low temperatures, the temperature dependence of linewidths has been determined both theoretically and experimentally.     

The pentad rotation-vibrational states of 12CD4: Wavenumber analysis of infrared and Raman spectra of the ν1, ν3, 2ν2, ν2 + ν4, and 2ν4 bands

The so-called pentad of ¹²CD₄ consists of the vibrational states v₁ = 1(symmetry A₁), v₃ = 1(F₂), v₂ = 2(A₁ + E), v₂ = v₄ = 1(F₁ + F₂), and v₄ = 2(A₁ + E + F₂). All states are located in the 1950 to 2250-cm^?1 region and all are strongly interacting. In the present work we have assigned more than 5000 infrared rotation-vibrational transitions and 163 isotropic Raman transitions from the vibrational ground state to the pentad. We have used infrared and Raman spectra of a resolution better than 0.01 cm^?1. From the experimental wavenumbers 2567 pentad rotation-vibrational energy levels with J ≦ 20 have been determined. These levels are reported in the paper. The levels have been used for refinements of the spectroscopic constants of two physically different effective Hamiltonians for the pentad states. For all levels with J ≦ 12 an unweighted standard deviation of 0.004 cm^?1 is obtained for both Hamiltonians, whereas the standard deviation increases more or less rapidly with J above 12 due to the imperfections of the Hamiltonians. The values of the spectroscopic constants of both Hamiltonians (85 and 106, respectively) are reported and the effects of the approximations are discussed.     

Magnetic phase transition in CsVF4

Magnetization and specific heat measurements are reported on the quasi two-dimensional antiferromagnet CsVF₄. Diverging magnetic susceptibility and specific heat at the Néel temperature are observed in a weak field along the crystallographic c-direction, but with increasing field they are progressively smeared. A hysteresis is observed in dc magnetization below the temperature at which M/H reaches a maximum. We present a possible explanation for these phase transition phenomena from the point of view that this compound is composed of two crystallographically inequivalent magnetic sites.     

Oscillatory behaviour of ultrasonic attenuation in KH2PO4 near the phase transition temperature

Oscillations in ultrasonic attenuation have been observed in KH₂PO₄ near the ferroelectric phase transition temperature for longitudinal ultrasonic wave propagation along the polarization axis. Oscillations are present both above and below the transition temperature; the periods of oscillations are different in the two phases for the same ultrasonic frequency and the same ∣T ? T_c∣. The temperature dependence of the oscillations shows that they are due to the phase transition.     

Electron paramagnetic resonance in Y1−cH1.92:Erc

We have investigated the EPR of isotopically enriched ¹⁶⁸Er³⁺ in Y_1?cH_1.92:Er_c where c = 100 and 1400 ppm, at both 1.4 and 9 GHz and between 1.5 and 50 K. Resonance lines were observed from Er³⁺ ions in both sites of cubic symmetry and sites of axial symmetry. We determine the numbers of Er³⁺ in cubic, and C_4v axial symmetry to be in the ratio 2:1. The cubic site resonance line is at g = 6.85 ± 0.07 and is attributed to a Γ₇ doublet. The linewidth has a linear thermal broadening of 3.9 ± 0.05 gauss K^-1 below circa 7 K. From the nonlinear thermal broadening above this temperature we determine the first excited state, in the cubic crystal field scheme, to be a Γ₈ at 35 ± 10 K above the Γ₇ ground state. We have investigated the origins of the (T = 0) residual linewidth for the ions in cubic symmetry, and conclude there to be a small but significant contribution due to unresolved transferred hyperfine structure from the surrounding hydrogen nuclei.     

New phase transition in LiKSO4

A subtle first order phase transition in LiKSO₄ has been discovered with the help of a temperature dependent study of the Raman intensity measurements of certain polar modes in different polarization configurations. The room temperature hexagonal C⁶₆ (P6₃) phase transforms to trigonal C⁴_3v (P31c) phase at 201°K while cooling; the reverse transformation (on heating) takes place at 242°K. The phase transition appears to be primarily associated with a cooperative reorientation of SO₄ tetrahedra in the crystal.     

Analysis of the ν2 and ν4 infrared bands of CD4

The infrared spectrum of totally deuterated methane CD₄ has been recorded between 930 cm^?1 and 1180 cm^?1 under high resolution (0.003 cm^?1). The ν₂ and ν₄ bands of ¹²CD₄ have been reanalyzed on the basis of a complete third-order Hamiltonian including all the coupling terms linking the upper states of the two bands. A set of only 16 self-consistent parameters have been adjusted to fit more than 1650 assigned transitions reaching a maximum upper state J value of 20. The obtained standard deviation is 0.0041 cm^?1. In addition, 171 lines of the ν₄ band of ¹³CD₄ have been assigned. They have been analyzed, in the same dyad scheme, by adjusting 7 parameters of the ν₄ band together with the main ζ₂₄ Coriolis parameter. The obtained standard deviation is only 0.0012 cm^?1.