A Raman and NMR study of KSbF6

The ¹⁹F spin-lattice relaxation results in the laboratory frame show that upon cooling from the tetragonal phase, KSbF₆(I), the transition to the cubic phase, KSbF₆(II), occurs over a wide temperature range (~38 K) in which the two phases co-exist. The Raman results using powdered samples agree with this observation but co-existence of phases has of course not been observed in single crystal Raman measurements. Upon rapid cooling of the powdered samples in the Raman studies the tetragonal phase could be super-cooled. Upon heating from the cubic phase, the transition was observed at 302 ± 2 K in all the measurements. The Raman spectra of KSbF₆(I) give no evidence of a non-centrosymmetric structure but it is shown that this is so because the Sb-atoms are only very slightly displaced from centro-symmetrical positions. ¹⁹F second moment results are in agreement with a model in which the SbF^?₆-octahedra are stationary below 180 K and reorient isotropically above 260 K. The importance of scalar spin-spin coupling between fluorine and antimony nuclei is reflected by the T_1p results in the vicinity of the T₁ minimum. The Raman spectra of the cubic phase at higher and lower temperatures are different and the polarized spectra of single crystals are used to assign the bands in terms of a C₃-site group symmetry for the SbF^?₆-groups and a T unit cell group symmetry.     

Optical properties of nanodiamond layers

Thin ultradisperse diamond (UDD) layers deposited from a water suspension are studied by optical and x-ray photoelectron spectroscopy (XPS). The effective band gap determined by the 10⁴-cm^?1 criterion for ozone-cleaned UDD is 3.5 eV. The broad structureless photoluminescence band (380–520 nm) is associated with radiative recombination through a system of continuously distributed energy levels in the band gap of diamond nanoclusters. The optical absorption of the material at 250–1000 nm originates from absorption on the disordered nanocluster surface containing threefold-coordinated carbon. The surface of UDD clusters subjected to acid cleaning contains nitrogen-oxygen complexes adsorbed in the form of NO ₃ ^? nitrate ions. Annealing in a hydrogen atmosphere results in desorption of the nitrate ions from the cluster surface. The evolution of the oxygen (O1s) and nitrogen (N1s) lines in the XPS spectra under annealing of a UDD layer is studied comprehensively.     

Magnetic phase transitions in the 1D ising antiferromagnet CsCoCl3

We report on Raman scattering from the magnons in CsCoCl₃ with particular emphasis on two magnetic phase transitions occurring at T_N = 20.82 K and at 8 K. The T → 0 magnon spectrum is fitted by a $\text{S =}\text{1}\text{2}$ anisotropic Heisenberg model. With a simple cluster model we can explain the temperature behaviour of the magnon frequencies and intensities. The physics of the 8 K phase transition is also discussed.     

Phase transitions in RbCaF3. I: Optical studies

Phase transitions in RbCaF₃ have been investigated by optical birefringence measurements and Raman scattering experiments. A near discontinuity in the onset of spontaneous birefringence at 196 K shows that the cubic to tetragonal phase change is “slightly” first order. The Raman spectra of the tetragonal phase support a D¹⁸_4h structure in which two phonons of A_1g and E_g symmetry soften as the 196 K transition is approached from lower temperatures. A very slow transition to a lower symmetry structure was observed at about 42 K in the Raman measurements.     

Effect of hydrogen on the structure of ultradisperse diamond

The paper reports on a study of the effect of annealing in hydrogen on the structural phase transition in clusters of ultradisperse diamond (UDD) obtained by the detonation method. The samples studied were of two types, namely, prepared by the “dry” and “wet” techniques, which differ in the cooling rate of the detonation products and, accordingly, in the structure of the diamond nanocluster shell. It is shown that, irrespective of the type of synthesis, the relative content of the diamond (sp3) phase increases within the anneal temperature range of 450 to 750°C, the increase being more pronounced in the samples prepared by “dry” synthesis. A model accounting for the observed structural transformation processes is discussed. A hypothesis of the possibility of compacting UDD clusters into bulk single crystals is put forward.     

Size-dependent nanodiamond-graphite phase transition at 8 GPa

The size-dependent diamond-graphite phase transition was detected in the course of a study of the growth of nanosized diamond particles under conditions of thermal treatment at 8 GPa. It was found that a critical size of diamond nanoparticles, on reaching which they transformed into graphite, was reached at 1623 K and a treatment time of 60 s, and it was equal to ～18 nm. The activation energy of the solid-phase growth of nanosized diamond particles at 8 GPa was determined to be 112±8 kJ/mol.     

Universal structural phase transition in network glasses

Raman and Mössbauer spectroscopy provide evidence for a transition from a molecular cluster network at x=0 to a continuous network at x=0.35 in Ge_1?xSn_xSe₂ alloy glasses. The nature of this morphological transition involves a reformation of molecular cluster surfaces in the heterogeneous phase to yield a homogeneous phase. The transition is believed to be a universal property of the easy glass formers and can be effected in one of several ways.     

Vibrational spectroscopy at very high pressures—XX Raman and far-IR study of the phase transition in paratellurite

Raman and far-IR spectra have been obtained up to ca. 45 kbar [4.5 GPa] for paratellurite (Te0₂) in a diamond anvil cell. At the D₄⁴ to D₂⁴ phase transition ca. 9 kbar an E symmetry mode initially at 122cm^?1 was found to split into two components in both IR and Raman spectra: their coincidence in both types of spectra shows that one component in the Raman spectrum cannot be an LO mode. No other E modes were seen to split. A further phase transition claimed ca. 30 kbar was not confirmed.Paratellurite is exceptionally sensitive to the presence of non-hydrostatic stresses, which greatly influence the phonon frequencies. This behaviour is illustrated by Raman spectra obtained under varying degrees of shear stress.     

Raman and IR study of high-pressure atomic phase of nitrogen

Atomic phase of nitrogen has been studied up to pressure 250 GPa and temperature 3300 K using a shear diamond anvil cell. This phase was synthesized both from azide NaN₃ and molecular N₂. The atomic phase has been interpreted as a cubic gauche (CG) structure by means of Raman and IR absorption spectroscopy procedures. The phase transition to CG begins at pressure 50 GPa and room temperature for NaN₃ and at 127 GPa for N₂. Observed pressure dependencies and degeneration of phonon modes, the selection rules for IR and Raman spectra, as well equilibrium pressure between molecular N₂ and atomic phase of nitrogen agree well with theoretical predictions for CG.     

A thermal and Raman investigation of the phase transitions above room temperature in anhydrous potassium acetate

Results using thermal and Raman techniques are presented on the phase transition in potassium acetate occurring above room temperature. Two phase transitions are observed at T_c1 = 349K and T_c2 = 413K. The magnitude of the entropy change at T_c1 and the Raman results suggest that this transition is orientational in nature and is due to rotation of the acetate ion about the c-c axis. The T_c2 transition is displacive in nature, and the Raman results show a marked softening of the lowest frequency mode as T_c2 is approached from below.     

Pressure and temperature induced modification of luminescence from tetracene single crystals

Fluorescence spectra of crystalline tetracene have been recorded in the temperature range 120 to 300 K under hydrostatic pressure up to 600 MPa. From discontinuities in both emission spectra and spectral intensities it is concluded that two phase transitions occur. The room temperature phase is transformed to a low temperature phase/high pressure phase I at T^I_t (p = 0) = 182 K, the temperature coefficient being dT^I_t/dp = 0.395 K/MPa. The phase transition is induced by a decrease of the specific volume under pressure and/or upon cooling. Lack of a significant shift of the origin of the fluorescence band near T^I_t at constant pressure is an artifact resulting from the neglect of reabsorption effects. The Stokes shift is 260 cm^-1, independent of temperature and crystal modification. In accord with previous Raman data a second phase transition occurs at T^II_t (p) = 143 K, the pressure shift being dT^II_t/dp = 0.088 K/MPa.In addition, the shift of the triplet energy as a function of pressure as well as the pressure-dependence of the rate constants governing fission of a singlet exciton into a pair of triplets is discussed utilizing their magnetic field dependences.     

Variable-temperature Raman scattering and X-ray diffraction studies of Bi3.25Nd0.75Ti3O12 ceramics

Neodymium-substituted bismuth titanate (Bi_3.25Nd_0.75Ti₃O₁₂, BNT_0.75) ceramics was prepared by chemical co-precipitation along with calcinations. The lattice instability has been investigated by variable-temperature Raman scattering and X-ray diffraction. The results showed that there was an orthorhombic to pseudo-tetragonal phase transition at about 695 K, in terms of the evolution of temperature dependence of Raman scattering frequencies. Some changes at about 695 K in the XRD lines, the lattice parameters (a, b, and c) as well as the orthorhombic distortion b/a have been detected in the high temperature X-ray diffraction, which confirmed the conclusion that the BNT_0.75 ceramics undergoes a ferroelectric to paraelectric phase transition at about 695 K.     

Raman scattering investigation of ferroelastic Sb5O7I crystals

Sb₅O₇I undergoes a displacive phase transition at 481 K where the symmetry is changed fromC _6h ² toC _2h ⁵ . In the low temperature monoclinic phase the crystal is ferroelastic. The polarized Raman spectra of Sb₅O₇I have been measured at various temperatures below and above the phase transition. The frequencies and symmetries of most of the theoretically expected Raman active phonons in the ferroelastic phase have been determined. The observation of a soft mode in the ferroelastic phase which disappears above the phase transition together with the fact that the unit cell of the ferroelastic phase is twice as large as that of the paraelastic structure permits the conclusion that the phase transition results from a phonon instability at the Brillouin zone boundaryM-point of the hexagonal phase. The temperature dependent splittings and intensity changes of several Raman lines are discussed with respect to the ferroelastic property of the crystal and the phase transition.     

Raman spectroscopic study of the lattice dynamics in the Rb2KMoO3F3 oxyfluoride

The lattice dynamics of the Rb₂KMoO₃F₃ oxyfluoride has been studied by Raman spectroscopy in the temperature range 7–400 K. A phase transition has been revealed at T ≈ 185 K with decreasing temperature. Anomalies of the frequencies and Raman line half-widths have been analyzed. No condensation of soft lattice modes has been found. The character of changes in the Raman spectra of the Rb₂KMoO₃F₃ oxyfluoride shows that the phase transition is related to variations in the [MoO₃F₃]^3? molecular octahedron.     

Central peak in the strontium titanate crystal near the tetragonal-to-cubic phase transition

Raman spectra of the SrTiO3 crystal have been measured in wide temperature (22?C316 K) and frequency (2?C1020 cm^?1) ranges. It has been shown that a central peak appears in low-frequency Raman spectra at temperatures above 70 K. In the spectral geometry with polarization rotation near the temperature T _c = 106 K of the cubic-to-tetragonal phase transition, the central peak exhibits properties of the order-disorder phase transition. Such a behavior of the central peak has been explained by the interaction of the low-frequency soft mode E _g with the relaxation mode near T _c .     

Mössbauer study on the magnetic field-induced insulator-to-metal transition in perovskite Eu0.6Sr0.4MnO3

We have investigated the spin dynamics of a distorted perovskite Eu_0.6Sr_0.4MnO₃ by means of Mössbauer spectroscopy. Below 70 K the exchange interaction grows gradually, and below 42 K the spins turn into a cluster glass state. The magnetic field-induced insulator-to-metal (IM) transition at low temperature is a transition from cluster glass to ferromagnet. The induced metallic phase seems to be still in non-uniform electronic state. On the other hand, at 80 K, just above T _c of the induced ferromagnet, a metamagnetic transition was observed.     

Raman scattering and X-ray diffraction study of structural phase transitions in the perovskite-type layer compound (C3H7NH3)2CdCl4

The structural phase transitions of (C₃H₇NH₃)₂CdCl₄ (PACC) have been studied by means of Raman scattering. X-ray diffraction and DSC measurements It is shown that the order-disorder phase transition Abma ? Pbca occurs at 156 K and not at 183 K as previously proposed by Chapuis (Acta CrystB34, 1506 (1978)) Apparently, the transition at 183 K does not change the Abma space group; it is suggested that it could be related to the occurrence of an incommensurate phase Another structural transformation of PACC is detected at 114 K, but no conclusion can be given as far as the structure of the low-temperature phase is not determined.     

Structural characterization,thermal, vibrational properties and molecular motions in perovskite-type diaminopropanetetrachlorocadmate NH3(CH2)3NH3CdCl4 crystal

The work presents a detailed analysis of the sequencing of the structural phase transitions in NH₃(CH₂)₃NH₃CdCl₄ crystal by differential scanning calorimetry (DSC), X-ray, infrared, far infrared and Raman spectroscopy. DSC studies have shown that in analyzed crystal occurring one reversible continuous phase transition at 375/374 K (on heating/cooling). Observed in Nujol and Fluorolube mulls in the wide temperature range between 296 K and 413 K spectral changes through the structural phase transition can be attributed to an onset of motion of cations. An assignment of some bands due to internal modes has been also proposed.     

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.     

Phase transition and structure of (C3N2H5)2SbF5 single crystal

New crystal of the formula (C₃N₂H₅)₂SbF₅ was obtained and characterized with DSC, DTA, TGA, structural and dielectric studies. DSC and dielectric studies revealed a structural phase transition of the first order at 216 K on cooling and 220 K on heating. The entropy of the transition ΔS equal to 11.5 J/mol·K gives evidence that the phase transition is order-disorder type. X-ray studies showed that transition undergoes from orthorhombic phase I with a space group of Pmmn to monoclinic phase II with a space group P2₁/m. The phase transition is proposed to be ferroelastic type. The molecular mechanism of the phase transition is related to ordering of imidazolium cations in phase II that are disordered in phase I.