Resonant Raman scattering in polyacetylene under hydrostatic pressure

The results of resonant Raman scattering experiments on trans-poly-acetylene under hydrostatic pressure are reported. The measurements were performed in a diamond anvil cell. The spectra could be measured up to 44 kbar. The pressure dependence of the 1295 cm^-1 line was measured in a sapphire cell up to 17 kbar. The results show that the changes in the phonon frequencies are very small. By comparing the pressure dependence of the Raman bands with their dependence on the photon energy of the exciting laser line it is possible to determine the pressure variation of the electronic energy gap. The results are consistent with previous measurements of the absorption spectrum under hydrostatic pressure which were carried out up to 13.5 kbar. The gap is found to decrease rapidly with pressure but the decrease tends to saturate at high pressures. The results are consistent with a model in which chain-chain interaction plays a dominant role.     

用高压显微光谱系统研究(Zn0.85Cd0.15)S:Cu,Al磷光体在流体静压力下施主-受主对的发光

用金刚石对顶砧高压显微光谱系统在室温和1bar—66kbar的流体静压力范围内研究了(Zn_0.85Cd_0.15)S:Cu,Al磷光体的发光峰位置和相对发光强度随压力而变化的规律。随着压力的增加,发射峰值波长迅速移向短波方向,而发射峰值对应的光子能量随压力增加的速率为4.7meV/kbar(38cm^-1/kbar)。这个值比该材料的吸收边随压力增加的速率要小。随着压力的增加,该磷光体的发光峰值相对强度急骤下降,当压力从常压升到66kbar时,发光峰值相对强度下降到原值的6％。这些结果可以用Al³⁺-Cu⁺的施主-受主对模型来解释。本文还估计施主(Al³⁺)和受主(Cu⁺)的激活能之和随压力增加的速率为3.7meV/kbar(30cm^-1/kbar)。 关键词：     

Production of nitrogen-free, hyperpolarized 129Xe gas

129 Xe with a nuclear polarization far above the thermal equilibrium value (hyperpolarized) is used in NMR studies to increase sensitivity. Gaseous, adsorbed, or dissolved xenon is utilized in physical, chemical, and medical applications. With the aim in mind to study single-crystal surfaces by NMR of adsorbed hyperpolarized ¹²⁹Xe, three problems have to be solved. The reliable production of ¹²⁹Xe with highest nuclear polarization possible, the separation of the xenon gas from the necessary quench gas nitrogen without polarization loss, and the dosing/delivery of small amounts of polarized xenon gas to a sample surface. Here we describe an optical pumping setup that regularly produces xenon gas with a ¹²⁹Xe nuclear polarization of 0.7(±0.07). We show that a freeze–pump–thaw separation of xenon and nitrogen is feasible without a significant loss in xenon polarization. The nitrogen partial pressure can be suppressed by a factor of 400 in a single separation cycle. Dosing is achieved by using the low vapor pressure of a frozen hyperpolarized xenon sample. Received: 12 June 1998     

Experimental equations of state for the rare gas solids

Piston-displacement equations of state (EOS) for the rare gas solids neon, argon, krypton and xenon have been determined to 20 kbar at temperatures from 4.2 K to the triple point in each case, with V(P,T) relations which are believed to be accurate to roughly 0.1 per cent. The present paper describes the results for the three heavier solids, argon, krypton and xenon, and indicates consistency between these results and other low pressure experiments at all temperatures. In particular, the individual isotherms can be represented by P(V) relations which are suggested by the form of the Lennard-Jones potential, the bulk moduli are only slightly temperature dependent at constant volume, and the data for the three solids appear to obey a reduced EOS both at T = 0 and near the triple point.     

Raman and mid-infrared spectroscopic study of the phase transitions in octafluoronaphthalene at elevated pressures

Raman and mid-infrared spectra of C₁₀F₈ have been obtained under hydrostatic pressures up to 17 kbar in a diamond anvil cell. The C₁₀F₈ I–II phase change, previously observed by neutron diffraction at about 0.8 kbar, has been confirmed. No evidence was found to support the existence of a furtt ier phase change between 4 and 6 kbar indicated by the neutron work, although this is certainly not precluded as the extra spectral features expected in this case are extremely small. The mode Grüneisen parameters, γ_i, allow a clear distinction between internal and external molecular modes, and scale roughly in accord with Zallen's relation γ_i$\text{\$}\text{?}$v_i^?2.     

Effect of hydrostatic pressure on the phase transition of ferroelectric PbTiO3

The effect of hydrostatic pressure on the dielectric constant of the Nb-doped lead titanate ceramics was measured up to 60 kbar at room temperature. From the previously observed pressure dependence of lattice parameters and the present results, it is concluded that the tetragonality decreases linearly with a slope of ?7.6×10^?4/kbar and that the pressure dependence of the tetragonal-cubic transition temperature is ?8.4K/kbar.     

Measurement of diffusion coefficients in polystyrene using xenon-129 NMR

A sample of polystyrene beads, 18 μm in diameter, has been sealed in an NMR tube under 10 atm of xenon gas. Two dimensional,¹²⁹Xe NMR spectra show cross peaks between the resonances corresponding to xenon in the free gas and the sorbed state, indicating that appreciable exchange occurs during the mixing time of the NMR experiment. Selective saturation of the free gas resonance attenuates the integrated intensity of the sorbed xenon resonance as a function of saturation time, thus allowing the accurate measurement of the exchange rates between the gas and the sorbed states. A model has been developed using a slightly modified form of Crank’s treatment of diffusion in a sphere which allows for the accurate determination of the diffusion coefficient for xenon in the sorbed state. The diffusion coefficient for xenon in polystyrene at 25°C is determined to be 2.9·10^?9 cm²/s.     

The effect of pressure on lattice parameter,magnetic susceptibility and reflectivity of SmS

The lattice parameter of SmS single crystals has been measured under hydrostatic pressure up to 70 kbar. The fit for the metallic phase by means of the Birch equation gives an unusually large pressure derivative of the bulk modulus B' = 11 and hence a large pressure dependence of B. No change in the nonmagnetic intermediate valence state of Sm is observed up to 24 kbar as concluded from our magnetic susceptibility measurements. Reflectivity measurements under hydrostatic pressure p > 6.5 kbar show a small plasma edge shift (～0.08 eV) towards lower energy upon cooling from 77 to 4.2 K. Hence the low temperature resistivity anomaly is attributed to an enhanced conduction electron scattering.     

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.     

Ultrasonic velocities near the spin-reorientation transitions in ErFeO3 at high pressure

Longitudinal and shear sound velocities have been measured near the spin-reorientation transitions in ErFeO₃ at hydrostatic pressure up to 2.4 kbar. The results, which are analyzed in terms of a phenomenological theory with magnetoelastic coupling terms, show that hydrostatic pressure has a very small effect on the magnetic anisotropy constants.     

Neutron diffraction investigation of MnAs under high pressure

Powdered MnAs has been investigated by neutron diffraction in a pressure cryostat, at hydrostatic pressures up to 13 kbar and temperatures down to 4.2 K. It has been found that in the orthorhombic MnP type structure, which under pressure is retained at low temperature, a spiral magnetic structure with propagation vector τ_a = 0.125X2πX a¹ at 12.6 kbar is formed.     

Pressure-induced magnetic transition in Fe2P

The weak field ac susceptibility and the resistivity of Fe₂P single crystals were measured as functions of temperature from 4.2–300 K and as functions of hydrostatic pressures up to 20 kbar, using a newly designed clamp-type pressure cell. The Curie temperature, and the first-order transition temperature, decreased rapidly with increasing pressure, and ferromagnetism vanished at about 13 kbar at 0 K. A second-order transition temperature, as well as the first-order transition, appeared in the region below 170 K and above 5 kbar (triple point) and a new pressure-induced magnetic phase was found. The phase is proposed to be antiferromagnetic for reasons discussed in the paper.     

Configuration and Performance of a Mobile 129Xe Polarizer

A stand-alone, self-contained and transportable system for the polarization of ¹²⁹Xe by spin exchange optical pumping with Rb is described. This mobile polarizer may be operated in batch or continuous flow modes with medium amounts of hyperpolarized ¹²⁹Xe for spectroscopic or small animal applications. A key element is an online nuclear magnetic resonance module which facilitates continuous monitoring of polarization generation in the pumping cell as well as the calculation of the absolute ¹²⁹Xe polarization. The performance of the polarizer with respect to the crucial parameters temperature, xenon and nitrogen partial pressures, and the total gas flow is discussed. In batch mode the highest ¹²⁹Xe polarization of P_Xe = 40 % was achieved using 0.1 mbar xenon partial pressure. For a xenon flow of 6.5 and 26 mln/min, P _Xe = 25 % and P _Xe = 13 % were reached, respectively. The mobile polarizer may be a practical and efficient means to make the applicability of hyperpolarized ¹²⁹Xe more widespread.     

Pressure-induced reversal of the sign of the hydrostatic piezoelectric constant of lithium tantalate

Measurements of the piezoelectric polarization of lithium tantalate for hydrostatic pressures up to 26 kbar show that the hydrostatic piezoelectric constant decreases smoothly to zero at a pressure of 22 kbar. Above this pressure the piezoelectric constant smoothly changes sign. This is believed to be the first observation of such an effect.     

金属氢化物(AlH3)n的热中子非弹性散射谱

本文报道了铝的氢化物(AlH₃)_n在常压和高压50kbar两种情况下的非弹性散射中子能谱,观察到了一些精细结构。与Roszinski的红外吸收谱作比较,在600—1700cm^-1波段内基本一致。而我们还测到了红外方法难以测到的三个低频峰。没有观察到高压对该材料的热学性质和微观结构的影响。 关键词：     

The SrB4O7:Sm2+ optical sensor and the pressure homogeneization through thermal cycles in diamond anvil cells

Abstract

Preliminary results, up to 550 kbar, on a thermal-cycling relaxation process of the 4.Methanol-1.Ethanol pressure-transmitting medium, are presented. The homogeneization is monitored by linewidth measurements of the ⁵D₀-⁷F₀ emission line of SrB₄O₇:Sm²⁺, recently proposed as an “almost ideal” high pressure calibrant. Above 100 kbar at 20°C, the line broadens linearly with increaisng pressure. Upon heating, at a fixed pressure, the linewidth is reduced to a minimum (“hydrostatic”) value provided a sufficient temperature is reached and this narrowing is irreversible upon cooling. For T=300°C this relaxation is observed for P (250 kbar, incomplete at 340 kbar and not observed at 550 kbar.     

Pulsed-Field-Gradient Measurements of Time-Dependent Gas Diffusion

Pulsed-field-gradient NMR techniques are demonstrated for measurements of time-dependent gas diffusion. The standard PGSE technique and variants, applied to a free gas mixture of thermally polarized xenon and O₂, are found to provide a reproducible measure of the xenon diffusion coefficient (5.71 × 10⁻⁶m²s⁻¹for 1 atm of pure xenon), in excellent agreement with previous, non-NMR measurements. The utility of pulsed-field-gradient NMR techniques is demonstrated by the first measurement of time-dependent (i.e., restricted) gas diffusion inside a porous medium (a random pack of glass beads), with results that agree well with theory. Two modified NMR pulse sequences derived from the PGSE technique (named the Pulsed Gradient Echo, or PGE, and the Pulsed Gradient Multiple Spin Echo, or PGMSE) are also applied to measurements of time dependent diffusion of laser polarized xenon gas, with results in good agreement with previous measurements on thermally polarized gas. The PGMSE technique is found to be superior to the PGE method, and to standard PGSE techniques and variants, for efficiently measuring laser polarized noble gas diffusion over a wide range of diffusion times.     

Pressure dependence of the electric field gradient at Cd impurities in antimony

The electric field gradient at¹¹¹Cd in Antimony was studied at hydrostatic pressures up to 7 kbar at 150 K, 293 K and 473 K. The logarithmic pressure derivatives, dlnq/dP, were found to be –67, –37 and –26 Mbar^–1 respectively. The isotropic volume dependence derived from these values was found to be positive and largely responsible for the anomalous temperature dependence, previously observed.     

High Pressure Instrumentation: Low and Negative Pressures

Much work on semiconductors, soft solids and biological materials does not require the megabar capability of the diamond anvil cell; a few accurate kbar being all that may be required. Work in this range poses its own challenges, to make the experiments routine, safe and reliable, and well-calibrated. We contrast diamond anvil cells working at what for them is very low pressure, with traditional bombs working at what for them is dangerously high pressure. We describe our preferred solution, a single-diamond cell, and demonstrate its use with Raman data from ethanol under low pressure. Negative hydrostatic pressure cannot be obtained by traditional methods. However, we present data showing the Raman spectrum of ethanol apparently at the negative pressure of m 3 kbar.     

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.