Pressure dependence of 35Cl NQR in hexachloro- (N3P3Cl6) and octachloro- (N4P4Cl8) cyclophosphazenes

High pressure studies of 35Cl NQR in the hexachlorocyclophosphazene N3P3Cl6 and in the K- and T-forms of octachlorocyclophospha.

Pressure dependence of 35Cl nuclear quadrupole resonance in 2,5-, 2,6- and 3,5-dichlorophenols

Pressure dependence of the 35Cl Nuclear Quadrupole Resonances (N.Q.R.) in 2,5-, 2,6- and 3,5-dichlorophenols (DCP) has been studied up to a pressure of about 6·5 kbar at room temperature. While the pressure dependence of the two resonance lines in 2,6-DCP is essentially similar, the lower frequency line in 2,5-DCP is almost pressure independent and the higher frequency line shows a linear variation with pressure upto about 3·5 kbar but shows a negative pressure coefficient beyond this pressure. The two lines in 3,5-DCP have a non-linear pressure dependence with the curvature changing smoothly with pressure. The pressure coefficient for both lines becomes negative beyond a pressure of 5 kbar. The pressure dependence of the N.Q.R. frequencies is discussed in relation to intra- and inter-molecular contacts. Also, a thermodynamic analysis of the data is carried out to determine the constant volume temperature derivative of the N.Q.R. frequency.

Pressure dependence of chlorine nuclear quadrupole resonance in sodium chlorate

The pressure dependence of the chlorine NQR frequency in NaClo3 has been investigated up to 20 k bar hydrostatic pressure. A distinct break in slope in the pressure dependence of the resonance frequency is observed near 11 k bar. This is attributed to a phase transition reported earlier by Bridgman in this pressure region.

Temperature and pressure dependence of direct current electrical resistivity in the Na2O-ZnO-B2O3 glass system

Two series of glasses were prepared, xNa2O, yZnO, 100 - x - yB2O3 and 30 - xNa2O, xZnO, 70B2O3 (mol%). The temperature dependence of the direct current resistivity was measured from room temperature to about 700 K and in both series of glasses we observed a simple Arrhenius type of temperature dependence. However, the resistivity of the binary alkali glass increased steeply by as much as two orders of magnitude with the addition of even a small quantity of ZnO and remained virtually unaffected by further addition of ZnO. The resistivity decreases gradually with increasing pressure in Na2O-B2O3 but increases with increasing pressure with the addition of ZnO.

Temperature and pressure dependence of 35Cl NQR in NaClO3 and Ba(ClO3)2·H2O

Pressure and temperature dependence of 35Cl nuclear quadrupole resonance (NQR) has been investigated in NaClO3 and Ba(ClO3)2·H2O. NQR frequencies are measured in the temperature range 77–300 K and up to 5 kbar pressure. The torsional frequency of the ClO3 pyramid and its variation with both pressure and temperature are evaluated from the NQR frequencies under the harmonic approximation. In general, the pressure effect on the internal motions is found to be less in Ba (ClO3)2·H2O compared to NaClO3. When the samples are cooled to 77 K the pressure coeffecient of NQR frequency becomes nearly zero in sodium chlorate, whereas it retains a value of 6 kHz kbar−1 in barium chlorate. This behaviour follows from the fact that at 77K, the torsional frequency in NaClO3 is unaffected by the application of pressure while it increases at the rate 12 cm−1 kbar−1 in Ba(ClO3)2·H2O.

A molecular dynamics study and molecular level explanation of pressure dependence of ionic conductivity of potassium chloride in water

Experimental ionic conductivity of different alkali ions in water shows markedly different dependences on pressure. Existing theories such as that of Hubbard-Onsager are unable to explain these dependences on pressure of the ionic conductivity for all ions. We report molecular dynamics investigation of potassium chloride solution at low dilution in water at several pressures between 1 bar and 2 kbar. Two different potential models have been employed. One of the models successfully reproduces the experimentally observed trend in ionic conductivity of K+ ions in water over the 0.001-2 kbar range. We also propose a theoretical explanation, albeit at a qualitative level, to account for the dependence of ionic conductivity on pressure in terms of the previously studied Levitation Effect. It also provides a microscopic picture in terms of the pore network in liquid water.

Pressure dependence of singlet and triplet excitons in amorphous polymer semiconductors

We present optical studies of both singlet and triplet states of a ladder-type conjugated polymer as a function of hydrostatic pressure. The pressure coefficient of the triplet-triplet absorption is smaller compared to the pressure coefficient of the singlet excitation, highlighting the more localized nature of triplet excitons. The photoluminescence and phosphorescence energies red-shift at similar rates with increasing pressure, thus giving experimental evidence for the first time that the singlet-triplet splitting remains almost a constant under high pressure until 4GPa. The diffusion length of the triplet excitons decreases to a few hundred nm at high pressures, as compared with a few micrometers at atmospheric pressure. Copyright (C) EPLA, 2013

Pressure Dependence of Glass Transition in As2Te3 Glass

Amorphous solids prepared from their melt state exhibit glass transition phenomenon upon heating. Viscosity, specific heat, and thermal expansion coefficient of the amorphous solids show rapid changes at the glass transition temperature (T-g). Generally, application of high pressure increases the T-g and this increase (a positive dT(g)/dP) has been understood adequately with free volume and entropy models which are purely thermodynamic in origin. In this study, the electrical resistivity of semiconducting As2Te3 glass at high pressures as a function of temperature has been measured in a Bridgman anvil apparatus. Electrical resistivity showed a pronounced change at T-g. The T-g estimated from the slope change in the resistivity-temperature plot shows a decreasing trend (negative dT(g)/dP). The dT(g)/dP was found to be -2.36 degrees C/kbar for a linear fit and -2.99 degrees C/kbar for a polynomial fit in the pressure range 1 bar to 9 kbar. Chalcogenide glasses like Se, As2Se3, and As30Se30Te40 show a positive dT(g)/dP which is very well understood in terms of the thermodynamic models. The negative dT(g)/dP (which is generally uncommon in liquids) observed for As2Te3 glass is against the predictions of the thermodynamic models. The Adam-Gibbs model of viscosity suggests a direct relationship between the isothermal pressure derivative of viscosity and the relaxational expansion coefficient. When the sign of the thermal expansion coefficient is negative, dT(g)/dP = Delta k/Delta alpha will be less than zero, which can result in a negative dT(g)/dP. In general, chalcogenides rich in tellurium show a negative thermal expansion coefficient (NTE) in the supercooled and stable liquid states. Hence, the negative dT(g)/dP observed in this study can be understood on the basis of the Adams-Gibbs model. An electronic model proposed by deNeufville and Rockstad finds a linear relation between T-g and the optical band gap (E-g for covalent semiconducting glasses when they are grouped according to their average coordination number. The electrical band gap (Delta E) of As2Te3 glass decreases with pressure. The optical and electrical band gaps are related as Delta E-g = 2 Delta E; thus, a negative dT(g)/dP is expected when As2Te3 glass is subjected to high pressures. In this sense, As2Te3 is a unique glass where its variation of T-g with pressure can be understood by both electronic and thermodynamic models.

Ultra-sensitive pressure dependence of bandgap of rutile-GeO2 revealed by many body perturbation theory

The reported values of bandgap of rutile GeO2 calculated by the standard density functional theory within local-density approximation (LDA)/generalized gradient approximation (GGA) show a wide variation (similar to 2 eV), whose origin remains unresolved. Here, we investigate the reasons for this variation by studying the electronic structure of rutile-GeO2 using many-body perturbation theory within the GW framework. The bandgap as well as valence bandwidth at Gamma-point of rutile phase shows a strong dependence on volume change, which is independent of bandgap underestimation problem of LDA/GGA. This strong dependence originates from a change in hybridization among O-p and Ge-(s and p) orbitals. Furthermore, the parabolic nature of first conduction band along X-Gamma-M direction changes towards a linear dispersion with volume expansion. (C) 2015 AIP Publishing LLC.

Pressure-induced electronic and structural transformations in bulk gese2 glass

The pressure dependence of the electrical of the electrical resistivity of bulk GeSe2 glass shows a semiconductor-to-metal transition at 7 GPa pressure. The high pressure phase is examined using he x-ray diffractometer and is found to be crystalline, with a face-centered cubic structure having a =4.06A. The electrical conductivity has also been studied as a function of temperature at various pressures.

Effect of pressure on the electrical resistivity of bulk Ge20Te80 glass

An irreversible pressure induced semiconductor-to-metal transition in bulk Ge20Te80 glass is observed at about 5 GPa pressure. The high pressure phase has a face centered cubic structure with a lattice constant 6.42 A° as deduced by X-ray diffraction studies on the pressure quenched samples. The temperature and pressure dependence of the electrical resistivity confirms the observed transition to be a semiconductor-to-metal transition. The temperature dependence of thermo electric power is also reported.

High-pressure magnetic susceptibility of the intermediate valence system EuPd2Si2

The pressure dependence (0-7 kbar) of the magnetic susceptibility is reported for the intermediate valence system EuPd2Si2 in the temperature interval 77-300K. It is found that the thermally induced valence transition becomes more gradual on application of pressure The characteristic fluctuation temperature Tf, also seems to be pressure dependent.

Temperature- and pressure-dependent study of Cl-35 NQR frequency and spin lattice relaxation time in 2,3-dichloroanisole

The temperature and pressure dependence of Cl-35 NQR frequency and spin lattice relaxation time (T-1) were investigated in 2,3-dichloroanisole. Two NQR signals were observed throughout the temperature and pressure range studied. T-1 were measured in the temperature range from 77 to 300 K and from atmospheric pressure to 5 kbar. Relaxation was found to be due to the torsional motion of the molecule and also reorientation f motion of the CH3 group. T-1 versus temperature data were analyzed on the basis of Woessner and Gutowsky model, and the activation energy for the reorientation of the CH3 group was estimated. The temperature dependence of the average torsional lifetimes of the molecules and the transition probabilities were also obtained. NQR frequency shows a nonlinear behavior with pressure, indicating both dynamic and static effects of pressure. The pressure coefficients were observed to be positive for both the lines. A thermodynamic analysis of the data was carried out to determine the constant volume temperature coefficients of the NQR frequency. The variation of spin lattice time with pressure was very small, showing that the relaxation is mainly due to the torsional motions of the molecules. Copyright (C) 2010 John Wiley & Sons, Ltd.