Grüneisen parameter of NaCl at high compressions

A new method of determining the pressure dependence of the Grüneisen parameter is described. The measurements were carried out on NaCl to 33 kbar at room temperature using an end-loaded piston-cylinder apparatus. A fluid cell arrangement with Bridgman unsupported area seals was used. Changes of sample temperature associated with small adiabatic pressure changes were measured and the Grüneisen parameter could be calculated from the thermodynamic relationship $\text{γ = (}\text{K}{}_{\mathrm{s}}\text{T}\text{)(}\text{?T}\text{?P}\text{)}{}_{\mathrm{s}}$ where K_s is the adiabatic bulk modulus. Our results are in excellent agreement with those reported by Roberts and Ruppin [1] who calculated the pressure dependence of γ from thermodynamic and ultrasonic data and in excellent agreement with those reported by Hardy and Karo [2] who carried out a lattice-dynamical calculation.     

The effect of hydrostatic and uniaxial pressure on the elastic constants of cadmium

The third order elastic constants of the hep metal cadmium have been determined from measurements of the hydrostatic and uniaxial pressure dependences of the velocities of ultrasonic waves propagated through single crystals. The hydrostatic pressure dependences of the second order elastic constants have also been obtained. The compression of cadmium has been estimated by extrapolation of the data up to high pressures by using the Murnaghan equation of state. Using the generalised Grüneisen theory in the quasiharmonic approximation, the long wavelength acoustic mode Grüneisen parameters have been obtained; the mean acoustic mode parameter is compared with the thermal Grüneisen parameter. In general the anisotropy of the vibrational anharmonicity of the acoustic modes is found to be consistent with the deviation of the c/a ratio of cadmium from that expected for an ideally close-packed metal.     

Ultrasonic attenuation in aluminium

Second- and third-order elastic-constant data have been used to determine the Grüneisen mode, 〈γ〉, average-square Grüneisen constant, 〈γ²〉 and nonlinearity constant D, for Aluminium. The attenuation suffered by longitudinal ultrasonic wave propagating in 〈100〉 and 〈110〉 directions and shear wave polarized along 〈100〉 and 〈1$\text{1}$0〉 directions, due to phonon viscosity and thermoelastic phenomena have been evaluated from two different values of TOEM at 289°K and comparison with observed experimental results has been made also.     

The elastic behaviour of the ternary zincblende structure semiconductor CuGe2P3

A single crystal has been grown of CuGe₂P₃, a ternary semiconductor with a zincblende structure in which the copper and germanium atoms are randomly distributed on the cation sites. The second order elastic constants measured by the ultrasonic pulse echo overlap technique (C₁₁ = 13.66, C₁₂ = 6.17, C₄₄ = 6.66 and bulk modulus B = 8.67 in units of 10¹⁰Nm^?2 at 291 K) are closely similar to those of GaP and conform well to Keyes' correlation for zincblende structure crystals. The hydrostatic pressure derivatives of the second order elastic constants ($\text{?C}{}_{11}\text{?P}\text{= 4.40}$, $\text{?C}{}_{12}\text{?P}\text{= 3.9}$, $\text{?C}{}_{44}\text{?P}\text{= 0.93}$ and $\text{?B}\text{?P}\text{= 4.07}$) and the third order elastic constants (C₁₁₁ = ? 8.45, C₁₁₂ = ? 3.49, C₁₂₃ = ? 1.13, C₁₄₄ = ? 2.82, C₁₅₅ = ? 1.44 and C₄₅₆ = ? 0.69 in units of 10¹¹Nm^?2) also resemble those of GaP: even the anharmonicity of the long wavelength acoustic modes of this ternary semiconductor resembles that of its binary “parent” compound. The positive signs of the hydrostatic pressure derivatives and the negative signs of the third order elastic constants show that the acoustic modes at the long wavelength limit stiffen under pressure, an effect which is quantified here by computation of the mode Grüneisen parameters, which are all positive. The harmonic and anharmonic force constants, obtained in the valence force field model, fit well into the pattern shown by related zincblende structure compounds: the ratio ($\text{β}\text{α}$) for bond bending (β) to stretching (α) force constants is greater than 4:1; the dominating anharmonic force constant is γ: most of the anharmonicity is associated with nearest neighbour atoms. Analysis of the temperature dependence of the elastic constants on the basis of a simple anharmonic model again emphasises the similarity between the elastic behaviour of CuGe₂P₃ and GaP. The thermal expansion of CuGe₂P₃ varies almost linearly with temperature between 291 K and 1000 K, the linear coefficient of thermal expansion α being 8.21 ± 0.02 × 10^?6 °C^?1. The similar lattice parameters and elastic behaviour of CuGe₂P₃ and GaP indicate that semiconducting devices made of epitaxial deposits of CuGe₂P₃ on a GaP substrate should prove to be almost strain-free.     

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.     

Modified grüneisen and anderson-grüneisen relations for quasispherical molecular liquids

The validity of the expression for the Grüneisen parameter of liquids has been tested by obtaining expressions for the heat capacity ratio, isothermal and adiabatic Anderson-Grüneisen parameters,C ₁-parameter, Rao’s acoustical parameter, Beyer’s non-linearity parameter, and relate them to the Grüneisen parameter. The calculated values for five liquefied gases comparising of quasi-spherical molecules are reasonably satisfactory and explain the experimental results for the variation of heat capacity ratio, Beyer’s nonlinearity parameter andC ₁-parameter with temperature for liquid state. It is shown that the isochoric temperature derivative of the sound speed, specified heat ratio and the compressibility are dominant factors with significant contribution for influencing the thermo-acoustic properties of liquids.     

Pressure derivatives of the elastic moduli of strontium,barium and lead nitrate

The pressure derivatives of the elastic moduli of Sr(NO₃)₂, Ba(NO₃)₂ and Pb(NO₃)₂ single crystal, have been measured by the ultrasonic pulse superposition method. The results for Sr(NO₃)₂ and Pb(NO₃)₂ are similar in magnitude and character, while the ones for Ba(NO₃)₂ differ strongly, $\text{?c}{}_{11}\text{?P}$ and $\text{?c}{}_{12}\text{?P}$ even From the measured pressure derivatives, the mode Grüneisen gammas and the Grüneisen constant as a function of temperature have been determined, and the latter is correlated with the experimental values, deduced from thermal expansion. The explicit temperature dependence of the elastic moduli is calculated, and found to be always negative, increasing in absolute value from Sr(NO₃)₂ to Pb(NO₃)₂.     

The volume dependence of the Grüneisen parameter and crystal stability

Utilizing only the general features of the lattice structure and potential, the explicit volume dependence of the entire frequency spectrum is derived in terms of its zero pressure values. It is shown that even though the frequencies and the mode Grüneisen parameters depend on the various details of the interactions and lattice structure, their variation with volume can be relatively simple functions of the volume. A criterion for mode instability with pressure is established involving only the measured value of γ(kλ). The volume dependence of the high temperature Grüneisen parameter is derived utilizing the characteristics of the full frequency spectrum through the first two moments of the mode gammas and the results are applied to the alkali-halides.     

On the spectral frequency distribution of translational vibrations in a face-centered cubic lattice of the C60 fullerite

The spectral frequency distribution g(ω) of translational lattice vibrations in the face-centered cubic phase of the C₆₀ fullerite at T = 300 K is calculated by the superposition method. The contribution from the translational vibrations to the heat capacity C _V of the C₆₀ fullerite and the x-ray characteristic temperature gJ_R entering into the exponent of the Debye-Waller factor are determined using the calculated frequency distribution g(ω). The results of the calculations are in good agreement with experimental data. It is noted that the librational and intramolecular lattice vibrations observed in the C₆₀ fullerite do not contribute significantly to the temperature-induced decrease in the x-ray diffraction intensity at T = 300 K. The Grüneisen parameters γ_mod calculated from the x-ray diffraction data are consistent with the thermodynamic Grüneisen parameters γ_lat at temperatures T ≤ 80 K but substantially exceed those at T ≈ 300 K. New x-ray diffraction experiments are proposed for independently determining the anomalously large negative values of the parameter γ₀, which is actually an orientational analog of the Grüneisen parameter.     

Correlation of mode grüneisen parameter with the ratio of phonon frequencies in binary cubic compounds

A correlation formula between the mode Grüneisen parameter γ_j and the frequency ratio of LO and TO phonons is semiempirically derived and compared with the experimental values for a large number of cubic binary and few ternary compounds. This relationship is represented by a linear function of $\text{x}{}^2\text{(x=}\text{ω}{}_{\mathrm{<mtext>LO</mtext>}}\text{ω}{}_{\mathrm{<mtext>TO</mtext>}}\text{)}$.     

Four constant potential function of amorphous selenium and evaluation of its thermodynamic and acoustic properties

Litov and Anderson after various considerations suggested a four constant potential function for a-Se as well as a-As₂S₃. Hence we also used a four constant potential function with the sole purpose of applying this potential function to obtain several acoustic, thermodynamic and other properties. We calculated several acoustic properties of a-Se like second order elastic constants (SOECs), their pressure derivatives, the longitudinal and transverse Grüneisen constant by two different methods, phonon frequencies, absorption band position through the use of Nath-Smith-Delaunay’s equation, and the thermodynamic properties like heat capacity, bulk modulus, thermal Grüneisen constant, the pressure derivative of the bulk modulus (dK _T/dP=C ₁), the pressure derivative ofC ₁ which is related to Anderson-Grüneisen parameter, pressure derivative of Grüneisen constant namelyγ′ _g which is related to second Grüneisen constant, characteristics of phonon frequencies, potential energy function through the use of fitted parameters and third order elastic constants. Finally we calculatedK _T at the reduced density ofρ/ρ ₀=1.1.K _T is obtained from the potential function with the fitted parameters. In all the above cases the calculated values are found to be in good agreement with experiment wherever available. In this connection it is important to point out that we eliminated ‘C’ a constant in the potential function using the equilibrium condition as was done by Litovet al in a-Se and Gerlichet al in the case of a-As₂S₃ as all amorphous substances are isotropic as mentioned by several authors. We contemplate to calculate several other properties for a-Se and a-As₂S₃ and present them at a later stage.     

Anomalous low-frequency phonons in ZrB<Subscript>12</Subscript>

The influence of pressure and temperature on low-frequency lines (100–300 cm^–1) in Raman spectra of ZrB₁₂ and LuB₁₂ single crystals has been investigated. These spectral features have been identified as one-phonon and two-phonon excitations of the acoustic branches of the phonon spectrum. It has been found that the observed spectra of ZrB₁₂ single crystals are more structured and indicate the development of phonon anomalies with a decrease in the temperature. Despite the fact that the low-frequency features in the phonon spectrum of ZrB₁₂ are characterized by a high value of the isothermal Grüneisen parameter, their isobaric Grüneisen parameter has a negative value. This indicates large contributions from the fourth-order anharmonicity, which significantly exceed the volume effects. The appearance of narrow lines in the frequency range from 155 to 175 cm^–1 at temperatures T < 100 K suggests the possibility of a structural transition with an incomplete softening of the lattice.     

Experimental study of the Grüneisen parameter of a fullerite C60 single crystal near phase transitions at 90 and 260 K by the photoacoustic method

The behavior of the Grüneisen parameter of single-crystal fullerite C₆₀ has been studied experimentally near orientational phase transitions at 90 and 260 K. The measurements have been performed by the photoacoustic method using an automated photoacoustic device with laser excitation (the intensity was modulated by a harmonic law) and shadow piezoelectric detection. The temperature dependence of the relative change in the Grüneisen parameter in the fullerite C₆₀ single crystal has been measured near the phase transitions at 90 and 260 K. The results have been analyzed.     

The Grüneisen parameter γ of KBr,RbCl and Bi through high pressure phase transitions

High pressure values for the adiabatic pressure derivative of temperature $\text{(}\text{?T}\text{?P}\text{)}{}_{\mathrm{s}}$ have been obtained by measuring the temperature change caused by a small rapid increase in pressure. Values for KBr and RbCl in phases B1 and B2 and for Bi in phases I, II and III are given for T = 295 K. The Grüneisen parameter γ is given by $\text{γ =}\text{B}{}_{\mathrm{s}}\text{(}\text{?T}\text{?P}\text{)}{}_{\mathrm{s}}\text{T}$ where B_s is the adiabatic bulk modulus. Ultrasonic and statk compressibility data are used to estimate the pressure and phase dependence of B_s. Dramatic increases in both γ and (?T/?P)_s are observed as the pressure increases through a phase transition. Values for the logarithmic derivate $\text{q ≡ (? ln}\text{γ}\text{?}\text{ln V}{}_{\mathrm{T}}$ are given.     

Vibrational modes and phase transition of Si-Ge solid solution

We present the simplified treatment where the lattice vibrations of Si or Ge atoms in the Si-Ge solid solution are replaced with that of pure Si or Ge crystal at lattice constants of the alloy. Considering the volume effect on the force constants of the pure constituent, we obtain the phonon dispersion curves of the local and band modes for Si_0.91Ge_0.09 and Si_0.11Ge_0.89 systems and the concentration x-dependence of the local and band modes frequencies in the Si_1?xGe_x solid solutions. Then, from the calculation of the effective mode Grüneisen parameter γ_i for the average phonon modes in the Si_1?xGe_x systems, we obtain the predominant correlation between TA mode Grüneisen parameter γ^X_TA at the point X and the phase transition pressure P_t, and the softening of TA modes is related to the pressure-induced phase transition of the Si-Ge solid solution.     

Thermal expansion coefficient of GaAs and InP

The temperature dependence of the thermal expansion for GaAs and InP is investigated theoretically using the experimental pressure derivatives of elastic stiffness constants and phonon frequencies. The linear correlation between the transverse acoustical mode Grüneisen parameter γ^X_TA and the metallic transion pressure P_t obtained by Weinstein is not satisfied for GaAs and InP, but the observed thermal expansion of GaAs is well reproduced. In addition, the linear expansion coefficient of InP is predicted theoretically as a function of temperature. Then, the phonon dispersion curves of GaAs and InP at their covalent-metallic transition pressures are quantitatively shown.     

Temperature and pressure derivatives of elastic constants in single crystal Au-47.5 at.% Cd near martensitic phase transformation

The behavior of the elastic properties and their pressure derivatives near the martensitic transformation β→β′ was determined from sound velocity measurements at a frequency of 10 MHz, on a single crystal of Au-47.5 at.% Cd.The transformation of the β phase to the martensitic β' phase was obtained from the anisotropic elastic constants c₁₁, c₄₄ and c′, and their pressure derivatives. The behaviour of c₁₁ and c₄₄ is normal as a function of temperature, while the variation of c′ is positive with temperature. Before the β→β′ phase change the value of c′ is very small and exhibits high elastic anisotropy. The small value of c′ and the anisotropy were explained according to the crystallographic mechanism of the martensitic transformation and the Zener theory of instability of the b.c.c. structure. The pressure derivatives of c′ are negative and the variation of $\text{d}\text{c}{}_{44}\text{d}\text{P}$ with temperature is anomalous. This behavior can be explained by the influence of pressure on the transformation temperature, and by the instability of the β phase. It was found that the elastic constants c′ determine the mechanism of the transformation. From the pressure derivatives of c₁₁, c₄₄ and c′ the Grüneisen parameters for different modes of vibration were calculated. For the c′ mode the values are negative, for the c₄₄ mode the variation of the parameter with temperature is negative. This anomalous behavior can be explained as due to the anisotropic softening of the atom bonding on the (110) planes of the cubic structure, as a consequence of the phase transformation mechanism.     

Grüneisen parameter for HCP iron at extreme compression

The Thomas–Fermi approximation gives the Grüneisen parameter γ=γ_∞=1/2 for all materials at extreme compression (P→∞ or V→0). After re-analyzing the existing experimental data of volume dependence of Grüneisen parameter γ of hexagonal close-packed (HCP) iron, we find that γ=1/2+a(V/V ₀)^1/3+b(V/V ₀) ⁿ , where a, b and n are constants. Based on this new form of γ, the second Grüneisen parameter q, the Debye temperature θ_D and the shear sound velocity v _s of HCP iron are discussed in the present work. It is found that the zero pressure second Grüneisen parameter q ₀=0.654, which is consistent with the previously determined value of HCP iron for Earth's core physics from Dubrovinsky et al. The calculations for the Debye temperature and the shear sound velocity are also found to be in good agreement with the experimental data.     

The soft acoustic phonon mode and its relation to the martensitic transformation in In-Tl alloys

Phonon dispersion curves for indium and f.c.t. and f.c.c. indium-thallium alloys have been calculated using the optimised model potential theory. The presence of a soft acoustic mode along [110], polarised [1$\text{1}$0] has been established. The closer the alloy composition is to the phase boundary, the softer this mode becomes: $\text{1}\text{2}\text{(C}{}_{11}\text{–C}{}_{12}\text{)}$ tends towards zero, in agreement with experimental ultrasonic velocity data.