High pressure tuning of optical transitions in Mg[Pt(CN)4]·7H2O

Mg[Pt(CN)₄]·7H₂O belongs to the class of tetracyanoplatinates(II) which crystallize in columnar structures. In different M_x[Pt(CN)₄]·yH₂O (MCP) single crystals the in-chain Pt-Pt-distance R varies between 3.67 Å (NaCP) and 3.15 Å (MgCP). Two optical transitions can be observed in polarized emission with the electric field vector E either parallel or perpendicular to the columnar (c)-axis. Polarized emission spectra of MgCP are recorded under hydrostatic pressure up to p ≈ 18 kbar (at 295 K). The transition energy v?₆ can be tuned from 17,600 cm^-1 to about 12,000 cm^-1 (2.18-1.48 eV). The pressure induced red shift for the two transitions is: E 6 c: dv?₆/dp = -320±20 cm^-1/kbar, E ⊥ c: dv?_⊥/dp = -270±20 cm^-1/kbar. These values are discussed in the context of the known functional relationship (for ambient conditions) between v? and R.     

DX-Like behavior of Se-impurity centers in gasb under hydrostatic pressure

Abstract

Hall coefficient (R_H) and electrical resistivity measurements have been performed as a function of temperature (between 77 K and 300 K) and under hydrostatic pressures (up to 15 kbar) on a set of Se-doped GaSb samples with impurity concentrations in the range 8×10¹⁷ cm^?3 - 1×10¹⁸ cm^?3. With increasing pressure at 300 K, the electrons are strongly trapped into a resonant impurity level. The pressure induced occupation of this level leads to time-dependent effects at T<120 K. The activated thermal electron emission over a potential barrier E<sb>B = 300×30 meV gives clear evidence for a large lattice relaxation around the impurity centers characteristic for DX-like behavior.     

Comparison of the Raman pressure shift and the Raman temperature shift of benzene and diamond with the ruby soale

Abstract

In order to serve as substitute for the pressure ruby scale at high temperature, the breathing mode of bemsens (990 cm^?1) and the first order Raman mode of diamond (1333 cm^?1) have been studied as a function of pressure and temperature in the range of 0–15 GPa and 25–400°C. The diamond and bensene Raman frequency shifts are shoft to be of valuable use as a pressure scale at high temperature. A further advantage of bensene is to remain a suitable pressure transmitting medium up to 350°C and 15 GP.     

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：     

Use of smoke samples in diamond-anvil cells to measure pressure dependence of optical spectra: Application to the ZnO exciton

We present measurements of ZnO exciton peak energies, E₀, at pressures up to 107.3 kbar. Smoke samples consisting of randomly oriented single crystal particles were prepared by oxidizing metallic zinc in air and were collected on one diamond face of a Merrill-Bassett pressure cell. Pressures were measured by the ruby fluorescence technique. In the pressure range between 5 and 90 kbar, our results indicate a consistent linear dependence with dE₀/dP = 2.33 × 10^?3 eV kbar^?1 for both increasing and decreasing pressures. A mixed phase structure is suggested by the observed irregular peak shapes and measured pressure dependence for the sample that had been taken beyond ? 90 kbar where the transformation to the NaCl structure has been reported.     

Theoretical calculations of the R1 red shift of ruby under high pressure

The essentials of the pressure-dependent shifts of the ruby fluorescence lines can be understood by the concept of electron cloud expansion under pressure. By using this concept the relevant formulas for the red shift are derived. The calculated results for red shifts of the ruby R₁ line are in good agreement with the experimental data up to 1700 kbar.     

Conductivity of C60 fullerene crystals under dynamic compression up to 200 kbar

The conductivity σ of C₆₀ fullerene crystals is measured under quasi-isentropic loading by a spread shock wave to a pressure of 200 kbar at the initial temperatures 293 and 77 K. A sharp increase in σ by seven to eight orders of magnitude is detected: from 10^?6?10^?7 Ω^?1 cm^?1 at normal conditions to 5 Ω^?1 cm^?1 under pressure from 100 to 200 kbar. The conductivity of samples under pressure decreases with decreasing temperature, which is characteristic of semiconductors. On pressure release, σ regains its initial value.     

High pressure 17O NMR study of solvent exchange on square planar complexes: Water exchange on [Pd(dien)H2O]2+

Abstract

The water exchange reaction of [Pd(dien)H₂O]²⁺ (dien = diethylenetriamine) was studied as function of temperature (268-308 K) and pressure 0.1-197 MPa) using ₁₇O NMR techniques. The rate and activation parameters are: k_cx = 5100 s^?1 at 298 K; ΔH^# =38 kJ mol^?1; ΔS^# = -47 JK^?1 mol^?1; ΔV^# = -2.8 cm³ mol^?1 at 296 K. The results are discussed in reference to solvent exchange data for other Pt(II) and Pd(II) complexes, and are interpreted in terms of an associatively activated substitution process.     

Measurement of the continuum absorption coefficient of water vapor near 14400 cm−1 (0.694 μm)

The continuum absorption coefficient (CAC) of water vapor (k _cont) in the visible region is determined for the first time from the data of laboratory measurements. For this purpose, the absorption spectra of water vapor in the region 14395–14402 cm^?1 are recorded with the aid of a high-sensitivity photoacoustic spectrometer with a frequency-tunable single-pulse ruby laser, and the absorption measured in this transparency microwindow is compared with that calculated based on the HITRAN 2004 data bank. In the spectral region under study, k _cont = (0.53 ± 0.18) × 10^?9 cm^?1 mbar^?1 at a total pressure of a water vapor-nitrogen mixture of 1000 mbar and a temperature of 295 K. This value of the CAC is roughly 23% higher than the CAC value in the IO-CKD model of the continuum.     

Investigation of irradiated 1H-Benzo[b]pyrrole by ESR,thermal methods and learning algorithm

1H-Benzo[b]pyrrole samples were irradiated in the air with gamma source at 0.969?kGy per hour at room temperature for 24, 48 and 72?h. After irradiation, electron spin resonance, thermogravimetry analysis (TGA) and differential thermal analysis (DTA) measurements were immediately carried out on the irradiated and unirradiated samples. The ESR measurements were performed between 320 and 400?K. ESR spectra were recorded from the samples irradiated for 48 and 72?h. The obtained spectra were observed to be dependent on temperature. Two radical-type centres were detected on the sample. Detected radiation-induced radicals were attributed to R-^+?NH and R=^?CC₂H₂. The g-values and hyperfine constants were calculated by means of the experimental spectra. It was also determined from TGA spectrum that both the unirradiated and irradiated samples were decomposed at one step with the rising temperature. Moreover, a theoretical study was presented. Success of the machine learning methods was tested. It was found that bagging techniques, which are widely used in the machine learning literature, could optimise prediction accuracy noticeably.     

Low temperature electron irradiation of tellurium

Abstract

Tellurium single crystal samples with a hole concentration of 3 × 10¹⁴/cm² were irradiated at 10 K with electrons with an energy of 0.6 and 1 MeV. In the range investigated resistivity and Hall-coeficient R_H both decreased linearly with the integrated electron flux. The hole generation rate was 0.09 cm^?1 and 0.47 cm^?1 for 0.6 and 1 MeV electrons, respectively. The Hall-mobility R_H/P increased with irradiation.

Annealing of the radiation damage by raising the temperature clearly revealed three recovery stages in the resistivity- and Hall-data. At 180K p and R_H returned to their pre-irradiation values. The original Hall-mobility was already restored close to 90 K.

A more detailed study of the first recovery stage, which occurs at about 50 K, revealed an activation energy of 170±40meV. It is most likely, that the observed lattice defects are Frenkel-defects. There are indications, that the point defects interact with dislocations.     

Water vapor line shifts in the range 5000–5600 cm<Superscript>−1</Superscript> induced by the pressure of different buffer gases

The coefficients of the water vapor line shifts induced by the pressure of oxygen, nitrogen, and argon are measured and calculated in the spectral range from 5000 to 5600 cm^?1. The experimental data are obtained from the analysis of the absorption spectra of H₂O-O₂, H₂O-N₂, and H₂O-Ar mixtures measured on a Fourier spectrometer with a resolution of 0.007 cm^?1 in a wide pressure range of buffer gases at room temperature for an optical path length of 84.05 m. The calculations are performed according to the Anderson impact theory of broadening with the use of only one adjustable parameter—the effective mean dipole polarizability of the upper vibrational state. The shifts of one and the same lines induced by the pressure of different buffer gases are compared; the role played by different terms of the intermolecular potential in the formation of the shifts is analyzed.     

Pressure measurement using the R fluorescence peaks and 417 cm−1 Raman peak of an anvil in a sapphire-anvil cell

In this study, synthetic sapphire crystals were used as anvils, coupled with a metal gasket, in a Merrill–Bassett-type pressure cell (sapphire-anvil cell (SAC)). Quartz and ruby chips were compressed in the cell and used as pressure calibrators for the SAC. In the sample–anvil interface, the relationship of the frequency shifts of the R1, R2 and 417 cm^?1 peaks with pressure was studied. They were constructed as new pressure calibrators. To test the applicability of the newly calibrated SAC, the Raman spectra of dolomite and calcite were measured in situ at room temperature.     

Pressure and temperature dependence of Raman scattering and optical absorption in crystalline S4N4

Raman scattering and optical absorption in crystalline S₄N₄ have been measured both as a function of pressure at 295 K and low temperatures. Polarized single crystal Raman data were also obtained as an aid in the assignment of the Raman active phonons. The pressure coefficients of the Raman active external and S-S stretching modes show a discontinuity near 7 kbar indicative of a second order phase change. The optical absorption edge at about 2.5 eV of a sublimed film of S₄N₄ shows red shifts of 1.3 × 10^?5 eV bar^?1 and 6.3 × 10^?4 eV K^?1 with pressure and temperature respectively. In the light of these results, the electronic, vibrational and structural properties of the crystal are discussed.     

Pressure dependence of the absorption edge at the E0 gap of mocvd - Grown ZnTe films

Abstract

We have investigated the direct gap absorption of 1μm thick ZnTe-epilayers grown on GaAs substrates by metalorganic chemical vapour deposition (MOCVD). Free ZnTe-layers were obtained by selective etching. The absorption coefficient was measured up to about 50000 cm^?1 in a diamand anvil cell in the temperature range from 115–300 K. The spectra near the direct gap E₀ are dominated by a sharp excitonic structure. Its change with pressure is evaluated by a model which allows to determine the pressure shift of the gap energy dE₀/dP and the change of the Rydberg energies of the excitons dR*/dP.^[1]     

Light hole transport in a strained GaAs/In0.18Ga0.82As quantum well at high pressures

Abstract

Here we report what we believe to be the first observation of the pressure dependence of the light hole behavior in a modulation doped In_0.18Ga_0.82As/GaAs single strained quantum well grown by MBE. Transport measurements have been undertaken as a function of temperature (4–300K) and hydrostatic pressure (4–8kbar). Hole mobilities of ～17000 cm²/Vs have been obtained for sheet carrier densities of ～3.3×10¹¹ cm^?2. At low temperatures (<100K) persistent photogenerated holes have been observed. The hole mobility is found to decrease with increasing pressure at a rate intermediate between that typically observed for holes and electrons in bulk III-V semiconductors.     

Mößbauereffekt in FeCl2, FeSO4 und FeSO4 · 7 H2O

Mößbauereffect measurements were performed with FeCl₂, FeSO₄ and FeSO₄ · 7 H₂O in the temperature range between 5 and 300 ?K. The quadrupole splittings at 5 ?K were determined to be (1.300±0.027) mm/sec, (3.650±0.053) mm/sec, and (3.350±0.053) mm/sec respectively. From the temperature dependence of the quadrupole splittings it follows that in FeCl₂ the energy of the excited 3d-electron-level isδ=150 cm^?1, in FeSO₄ δ ₁=360 cm^?1 andδ ₂=1680 cm^?1 and in FeSO₄ · 7 H₂Oδ ₁=480 cm^?1 andδ ₂=1300 cm^?1. The magnitudes of the magnetic field at the iron nucleus at 5 ?K are (202±8) kOe for FeSO₄ and (0±4) kOe for FeCl₂.     

Raman spectroscopy of solid nitrogen up to 374 kbar

We measured the Raman spectrum of room-temperature solid nitrogen in a diamond cell at pressures up to 374 kbar. Only the molecular stretching mode was observed. The frequency of this mode appears to increase smoothly from 2340 cm^-1 at 39 kbar to 2394 cm^-1 at 374 kbar. Between about 50 and 120 kbar, the Raman line is split into a second, higher-frequency peak, which may be associated with molecular ordering in the solid. Measurements of broadening and splitting in fluorescence lines from the ruby pressure gauge indicate that solid nitrogen is reasonably plastic up to 130 kbar. We suggest that nitrogen might serve as a useful pressure medium.     

Properties of IR Absorption Spectra of Bi-Pb-Sr-Ca-Cu-O Superconducting Material

Abstract

We used the co-decomposition method to make the Bi(Pb)-Sr-Ca-Cu-O superconductor samples (T_c = 112K) under oxygen partial pressure. Oxygen dependence of high-T_c phase was studied. The infrared absorption spectra of (Bi_1?xPb_x)₂Sr₂Ca₂Cu₃O_10+σ superconductor were measured at various temperatures from 98 to 290K. A new IR absorption peak was observed at 1265 cm^?1 below 217K. The intensity of this peak became stronger with temperature decreasing.     

Temperature dependence of the Raman bandwidths and intensities of a lattice mode near the tricritical and second order phase transitions in NH4Cl

We calculate here the temperature dependence of the damping constant using the expressions derived from the Matsushita's theory and the temperature dependence of the order parameter from the molecular field theory for the tricritical (1.5?kbar) and second order (2.8?kbar) phase transitions in NH₄Cl. Our calculations are performed for the ν ₅ (174?cm^?1) Raman mode of NH₄Cl for the pressures studied. Predictions for the damping constant are in good agreement with our observed Raman bandwidths of this lattice mode for both pressures. The Raman intensities calculated from the molecular field theory by means of the order parameter are also in good agreement with our observed Raman intensities of the ν ₅ (174?cm^?1) mode for both tricritical (1.5?kbar) and second order (2.8?kbar) phase transitions in NH₄Cl. In this study our observed Raman intensities of this lattice mode are analysed using a power-law formula with the critical exponent β for the order parameter at those two pressures considered in NH₄Cl. From our analysis, the value of β?=?0.5 is obtained as the mean field value.