Structural study of ND4I at high pressures and low temperatures

Abstract

Structure, positional, and thermal parameters of ND₄I were studied at high pressures up to 90 kbar and low temperatures down to 10 K using time-of-flight neutron diffraction. The phase transition from a disordered CsCI-type cubic phase ND₄I(II) into a recently discovered high pressure phase ND₄I(V) was observed at P = 80(5) kbar. Surprisingly, the structure of the high pressure phase V was found to bear a strong resemblance to that of the ambient pressure, low-temperature phase III - tetragonal structure with an antiparallel ordering of ammonium ions, space group P4/nmm. The critical value of the deuterium positional parameter corresponding to the II-V transition is close to the one for the phase transition between the disordered and ordered CsCl-type cubic phases II and IV in other ammonium halides.     

1H NMR study of [N(CH3)4]2ZnCI4 at high pressures and low temperatures

Wide-line proton NMR studies on polycrystalline tetramethylammonium tetrachlorozincate have been carried out at high hydrostatic pressures up to 15 kbar in the temperature range 77-300 K and at ambient pressure down to 4.2 K. A second-moment transition is observed to occur starting around 161 K, the temperature for the V-VI phase transition. This transition temperature is seen to have a negative pressure coefficient up to 2 kbar, beyond which it changes sign. At 77 K the second moment decreases to 4 kbar and then increases again as a function of pressure. The results are explained in terms of the dynamics of the N(CH₃)₄ groups.     

Thermoelectric power of cerium at high pressures

The electronic phase transition in cerium occurring near 7 kbar pressure at room temperature which is attributed to the 4f–5d electron promotion has been studied using thermoelectric power as a tool. The important results that have emerged out of this work are: (a) the relatively large variation in the absolute thermoelectric power ofγ-cerium (normal fcc phase) with pressure prior to the phase transition (in contrast to the rather small resistivity change with pressure in this region); (b) a sharp decrease in the thermoelectric power accompanying the iso-structuralγ-α phase transition; and (c) the continuous decrease in the thermoelectric power ofα-cerium (collapsed fcc phase) with pressure, ultimately changing sign at higher pressures. An explanation based on the “virtual bound state” model is proposed to account for these results.     

Spectroscopy at very high pressures—XXV: The IR spectrum of ferrocene at high pressures

The IR spectrum of ferrocene has been examined up to 50kbar under approximately hydrostatic conditions in a gasketed diamond anvil cell, and also under shear stress without gaskets. The results provide evidence in support of Duecker and Lippincott's claim of a phase transition at about 11.5 ± 0.5 kbar which is sluggish except under shear stress. Thermal strain and phonon self-energy contributions to the temperature-induced frequency shifts were analysed but no general pattern emerged.     

Phase transitions in N—n-propylpyridinium-TCNQ2 and N—n-butylpyridinium-TCNQn at high pressures

The electrical resistivity of N-n-propylpyridinium-TCNQ₂ (NPPy-TCNQ₂) and N-n-butylpyridinium-TCNQ_n (NBPy-TCNQ_n) has been measured as a function of temperature and pressure. Phase transitions in these salts have been studied at high pressures. The transition temperature (T_c) in NPPy-TCNQ₂ at atmospheric pressure increased with increasing pressure at the rate of dT_c/dP = + 12.0 degkbar^?1. The value of volume change calculated from the Clapeylon-Clausius relation was + 4.4 cm³ mol^?1. The electrical resistivity along the a- and c-axis increased with increasing pressure below 7 kbar. This anomalous electrical behaviour is closely related to the crystal structure of NPPy-TCNQ₂. The resistivity dropped sharply at about 11 kbar. This abrupt change may be due to a new pressure induced phase transition.The T_c of the NBPy-TCNQ_n increased remarkably with increasing pressure up to 0.7 kbar, above which the phase transition disappeared. The phase transitions of N-n-alkyl-substituted pyridinium TCNQ salts depend strongly on the nature of cations.     

Raman spectra of forsterite and fayalite at high pressures and room temperature

Abstract

Raman spectra of the two pure end-members of olivine (forsterite and fayalite) were studied at high pressures and room temperature in a diamond-anvil cell using both single-crystals and polycrystalline samples in pressure mediums of either an ethanol-methanol mixture or H₂O. Variations with pressure were studied up to 170kbar for fayalite and to 300kbar for forsterite. Two intensive Raman bands of fayalite were definitely observable at high pressures, but only one of them can be reliably determined. Both have a linear variation within experimental uncertainty. Because of interference from the high spectral background, we found that nearly all the weak bands of forsterite could not be reliably determined at high pressures. However, the pressure variations of all bands of forsterite which can be reliably determined are non-linear. The rates of frequency change for the intense bands of forsterite determined in the present experiment are consistent with those of natural forsterites determined by Besson et al. ¹ and Gillet et al. ², but are in a slight discordance with those reported by Chopelas³. Furthermore, there is no evidence for the olivine ? spinel phase transition occurring at room temperature.     

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 study of rutile (TiO2) at high pressures

The Raman spectra and polymorphism of rutile have been investigated under hydrostatic pressures up to 90 kbar at room temperature. A transition previously observed in rutile at 30 kbar in a Drickamer-type cell under nonhydrostatic conditions was observed to begin at approximately 70 kbar in a 4:1 mixture of methanol and ethanol. The small amount (10–20%) of the high-pressure phase synthesized from rutile, however, did not increase even though the sample was left under pressure for a period of 1 month at ambient temperature. On the basis of factor group analysis, in situ powder x-ray diffraction data, and comparison of the Raman spectrum of the high-pressure modification with that of TiO₂-II (α-PbO₂-type structure synthesized from anatase powder at 40 kbar and 400°C), it is evident that a high pressures rutile transforms irreversibly to TiO₂-II.     

Raman study of NH4CI at high pressures

Abstract

The Raman spectrum of ammonium chloride has been carefully studied in the vicinity of its Λ-transition. Spectra were recorded as a function of temperature under various fixed pressures close to 1.6 kbar, which is the pressure required to make the Λ-transition become second order. The critical exponents derivable from the spectroscopic data seem to be as reliable as those from other types of data, even in the multicritical region.     

Differential thermal analysis at high pressures—VII: Phase behaviour of solid methanol up to 3kbar

The phase behaviour of solid methanol was investigated from -196°C to the melting temperature and up to 3 kbar, using a low-temperature high-pressure dta apparatus. The melting temperature rises from -98°C at 1 atm to -64°C at 2775 bar. Solid methanol exhibits a transition at atmospheric pressure at approximately -115°C; the transition has a strong tendency to superheat and to occur at -110°C. The transition temperature rises from approximately -115°C at 1 atm to -81°C at 2725 bar. Small impurities of water induce a “second transition” at -117.3°C that must be attributed to the water-methanol eutectic. Volume changes accompanying the phase transition have been calculated using the Clausius Clapeyron equation.     

The structure of FeCl2 at high pressures

A full three-dimensional structure determination of FeCl₂ has been performed at hydrostatic pressures up to 6.4 kbar at room temperature. These studies demonstrate the feasibility of four-circle neutron diffraction studies under pressure, and show that above 5.8 kbar FeCl₂ has a structure isomorphous to FeBr₂. The pressure dependence of chlorine position parameter and lattice parameters has been studied over the entire pressure range.     

Vibrational spectroscopy at very high pressures. Part 35.1 A Raman study of K2M(CN)4, (M = Zn,Cd, Hg)

Each of the complex cyanides K₂M(CN)₄, (M = Zn, Cd, Hg), shows two high pressure first-order phase transitions which have been characterized using Raman spectroscopy. The phase changes are at 1.5 and 8.5 kbar for M = Hg, 3 and 8 kbar for M = Cd, and 4 and 14 kbar for M = Zn. It is concluded that, for each material, phase II has the trigonally-distorted spinel structure of room temperature Rb₂Hg(CN)₄, whilst phase III is probably of the hausmanite type (a tetragonally-distorted spinel).     

Superconductivity in polymeric sulfur nitride (SN)x at high pressure

Investigations of the pressure dependence of the superconducting transition temperature T_c up to 17 kbar, and of the normal conductivity up to 50 kbar are reported. It is observed that below 8 kbar, the value of T_c increases linearly with the pressure. In addition, there is a significant drop of T_c at about 9 kbar which may be due to a phase transition.     

Neutron diffraction investigation of the structural transition in HgSe1−x Sx ternary mercury chalcogenide systems at high pressures

The structure of HgSe_1?x S_x ternary mercury chalcogenides at high pressures up to 35 kbar is investigated by neutron diffraction. It is found under pressure, that the HgSe_1?x S_x compounds undergo, a phase transition from the cubic sphalerite-type to the hexagonal cinnabar-type structure, which is accompanied by a jump-wise change in the unit cell volume and interatomic distances. The unit cell parameters and the positional parameters of Hg and Se (S) atoms in the high-pressure hexagonal phase are determined. A two-phase state is revealed in the phase transition region.     

Critical behaviour of Sn2P2S6 and Sn2P2(Se0.28S0.72)6 crystals under high hydrostatic pressures

Basing on the temperature dependences of optical birefringence for Sn₂P₂S₆ and Sn₂P₂(Se_0.28S_0.72)₆ crystals subjected to hydrostatic pressures, we prove unambiguously that Sn₂P₂S₆ reveals a tricritical point on its (p, T)-phase diagram with the coordinates (p, T) = (4.3 kbar, 259 K), so that the second-order phase transition transforms into the first-order one whenever the pressure increases above 4.3 kbar. We also find that increasing hydrostatic pressure applied to Sn₂P₂(Se_0.28S_0.72)₆ leads to the change in the phase transition character from tricritical to first order. Further increase in the pressure up to ~2.5 kbar imposes splitting of the first-order paraelectric-to-ferroelectric phase transition into two phase transitions, a second-order paraelectric-to-incommensurate one and a first-order incommensurate-to-ferroelectric transition.     

Vibrational spectroscopy at very high pressures. part 34.1 Raman spectra of polymorphs of mercuric cyanide

Phase transitions have been observed in mercuric cyanide near 2.5, 8, 19 and 60 kbar. The first four phases have been characterized by Raman spectroscopy. Phase II is closely related to the molecular parent phase I. The coordination at mercury appears to increase to four on entering phase III and phase IV has a spectrum consistent with the cubic structure related to anti-cuprite adopted at s.t.p. by Cd(CN)₂. Above 60 kbar deep brown Hg(CH)₂ V is formed irreversibly: it contains C =N rather than C≡N bonds.     

Phases of silicon at high pressure

X-ray diffraction studies are reported on silicon at pressures up to 250 kbar (25 GPa). A transition to the β-Sn structure (II) initiates at 112 ± 2 kbar and two phases (I + II) coexist to 125 ± 2 kbar. At 132 ± 2 kbar a new phase (V) initiates, and the transition is complete at 164 ± 5 kbar. This phase persists to 250 kbar. Its structure is tentatively assigned as primitive hexagonal with c/a = 0.941 ± 0.002 at 250 kbar. On release of pressure, the sequence is V → (V + II) (145 - 110 kbar) → II → (II + III) (108 - 85 kbar) → III, the last phase persisting to room pressure.     

Raman spectra of phase a at various pressures and temperatures

Variations of the Raman spectra of phase A (Mg₇Si₂O₁₄H₆) were investigated up to about 400 kbar at room temperature and in the range 80–853 K at atmospheric pressure. Phase A appears to undergo a reversible phase transition around 180 kbar at room temperature, and it becomes amorphous above 813 K at atmospheric pressure. The Raman frequencies of the two strong OH bands of phase A decrease linearly with increasing pressure, but increase non-linearly with increasing temperature. The frequencies of the other Raman bands of phase A increase non-linearly with increasing pressure but decrease both linearly and non-linearly with increasing temperature within the experimental uncertainties and the range investigated. The trends of the pressure and temperature effects on the Raman frequencies of phase A parallel those observed in the hydrous β-phase, but nonlinear behaviour was not observed in the latter.     

Superconductivity and phase stability of selenium at high pressures

Hexagonal Se shows no indication of a transformation to a metallic, superconducting phase up to 160 kbar. Amorphous Se transforms at about 130 kbar to an unstable metallic, superconducting state which anneals slowly at room temperature toward a non-metallic, non-superconducting phase. Monoclinic Se behaves much like amorphous Se. X-ray diffraction indicates that all samples are in the hexagonal phase after release of pressure.     

Features of the semiconductor-metal transition in GaAs at ultrahigh pressures: New intermediate phases

Using the thermopower method (Seebeck effect), the semiconductor-metal transition that occurs in gallium arsenide single crystals of n and p types at ultrahigh pressures P above ～11–18 GPa has been studied. It has been found that the transition in n-type samples begins at lower pressures. In the region of the semiconductor-metal phase transition, features have been observed on the thermopower dependences S(P). These features indicate that lattices intermediate between the initial semiconductor structure of zinc blende and the Cmcm high-pressure orthorhombic metallic phase are formed. By analogy with ZnTe, one intermediate phase (semiconductor with hole conductivity) is suggested to have the cinnabar structure and the second intermediate phase (semimetallic with electron conductivity) possibly has the SC16 structure. A model of the semiconductor-metal transition is discussed. The behavior of the thermoelectric properties in GaAs under pressure is compared with the behavior of these properties in other A_NB_8?N semiconductors, which also undergo the transition to the metallic state.