Investigation of phonon anomalies in intermediate valence compounds SmS and Sm0·65Y0·25S

Phonon anomalies in two intermediate valence compounds (IVC), SmS and Sm_0·75Y_0·25S have been investigated using breathing shell model (BSM). The BSM includes breathing motion of electron shells of the rare earth atom due tof−d hybridization. The phonon dispersion curves of IVC, calculated from the present model, agree well with the measured data. One-phonon density of states calculated from the present model compares well with the Raman spectra.     

Phonon properties of rare earth ytterbium pnictides

We report for the first time the complete phonon dispersion curves for the ytterbium pnictide compounds (YbN, YbP and YbAs) using a breathing shell model to establish their predominant ionic nature. The calculated results also show that this group of rare earth compounds does not show any elastic and phonon anomalies which are the characteristic features of other rare earth compounds. We emphasize the need for further Raman and neutron scattering measurements.     

Comparison of the molecular cluster model with the phonon model for Jahn—Teller active impurities in crystals

For comparing the molecular cluster model with the phonon model in describing the Jahn-Teller interaction for magnetic impurities in crystals, the Jahn-Teller energy and the Ham reduction factors are expressed in terms of the phonon Green's function of the host crystal for an orbital triplet coupled to E_g modes of vibrations. Numerical results for the case of MgO lattice have been obtained using the phonon Green's function derived from the breathing shell model.     

Ferroelectrics

A diatomic linear chain model is used to describe the dynamical properties of displacive type ferroelectric compounds. For these materials the non-bondingp-orbitals of the chalcogen ions play an essential role, which is taken into account by assuming a nonlinear fourth-order polarizability at the chalcogen-ion lattice site. Within the self-consistent phonon approximation soft modes, phonon dispersion curves, phonon anomalies and related quantities can be calculated for all temperatures. Going beyond the self-consistent phonon approximation, the model yields, in the continuum limit, interesting new solutions such as periodic non-linear waves, kinks, which describe the statics and dynamics of ferroelectric domain walls, and pulse solutions.Dedicated to Professor Harry Thomas on the occasion of his 60th birthday     

Many body interactions in binary ionic solids

Recent developments in phonon models and microscopic theories of lattice mechanics have been reviewed, with particular emphasis on binary ionic solids. In doing so, we have traced the evolution of many body interactions from the electron-shell deformation and charge-transfer mechanisms and the approach of their incorporation in the framework of a dipolar model to describe the lattice static, dynamic, and anharmonic behaviours of these solids. The essential background and formalism of the sophisticated lattice dynamical models thus developed have been thoroughly treated in order to make them understandable and establish interrelationships between phonon and microscopic models and among themselves. An assessment of the relative merit of these models (e.g. breathing shell model, deformable shell model and three-body-force shell model) has been performed by making a critical comparison of theoretical results obtained from their comparative and unified lattice mechanical investigations with those measured from the experimental techniques and extensively surveyed in this article. Finally, we have outlined the future prospects and the scope of extension of various phonon models in view of the current trends in lattice dynamics and needs for a comprehensive study of the defect and anharmonic properties exhibited by the crystalline solids.     

Lattice dynamics in mixed valent Rare Earth compounds

In the frame of a single coherent picture for the electron lattice interactions in mixed valent Rare Earth compounds, the phase diagrams and phonon dispersions are studied. Our model is introduced on a microscopic level and discussed in detail. The mechanism of the phase transition and the role of the lattice is illuminated and various properties are considered in a model calculation. Anomalies in the phonon dispersions of Sm_1–x Y _x S, which have recently been found, find a satisfying explanation.     

The intrinsic lifetime of low-frequency zone-centre phonon modes in silicon nanowires and carbon nanotubes

Estimates of the intrinsic lifetime of low-frequency zone-centre phonon modes in silicon nanowires and carbon nanotubes have been presented from the application of Fermi’s golden rule formula based upon an elastic continuum model for cubic anharmonicity. In particular, results have been presented for the lowest non-zero mode in both nanostructures, and also the breathing mode in the nanotube. Except for the ultrathin nanowire, the lifetime increases with size and decreases with an increase in temperature. Typically, these modes have a lifetime of the order of nanoseconds, almost a thousand times larger than the lifetimes of optical phonon modes in the corresponding bulk materials. Also, at room temperature the lifetime of the lowest non-zero mode is nearly an order of magnitude larger in the (20,20) nanotube than in the nanowire of similar thickness (width 2.2 nm).     

Vibronic Sidebands of Coherent Phonon States

Recently experiments have been reported about phonon sidebands in doped crystals, which may originate from coherent phonon states. The corresponding modes are either confined phonon modes in nanocrystals or localized phonon modes in bulk materials, both showing small damping due to phonon-phonon interaction. We present a theory of the lineshape of vibronic sideband spectra due to coherent phonon states using the conventional model of linear electron-phonon coupling and displaced equilibrium positions of the oscillators in the initial and final electronic states. Unlike in the conventional theory, the initial state of the oscillator is taken as a coherent phonon state and not as a thermalized one. Under these conditions we got an exact analytical solution for the lineshape of the vibronic sideband. The lineshape is determined by two parameters, the Huang-Rhys parameter S and the coherence parameter α of the phonon state. For α = 0 the lineshape converts into the standard Pekarian form for T = 0.     

Effect of pressure on the thermal expansion of MgO up to 200~GPa

Constant temperature and pressure molecular dynamics (MD) simulations are performed to investigate the thermal expansivity of MgO at high pressure, by using effective pair-wise potentials which consist of Coulomb, dispersion, and repulsion interactions that include polarization effects through the shell model (SM). In order to take into account non-central forces in crystals, the breathing shell model (BSM) is also introduced into the MD simulation. We present a comparison between the volume thermal expansion coefficient α dependences of pressure P at 300 and 2000~K that are obtained from the SM and BSM potentials and those derived from other experimental and theoretical methods in the case of MgO. Compared with the results obtained by using the SM potentials, the MD results obtained by using BSM potentials are more compressible. In an extended pressure and temperature range, the α value is also predicted. The properties of MgO in a pressure range of 0--200~GPa at temperatures up to 3500~K are summarized.     

Phonon and thermal properties of achiral single wall carbon nanotubes

A detailed theoretical study of the phonon and thermal properties of achiral single wall carbon nanotubes has been carried out using force constant model considering up to third nearest-neighbor interactions. We have calculated the phonon dispersions, density of states, radial breathing modes (RBM) and the specific heats for various zigzag and armchair nanotubes, with radii ranging from 2.8 Å to 11.0 Å. A comparative study of phonon spectrum with measured Raman data reveals that the number of Raman active modes for a tube does not depend on the number of atoms present in the unit cell but on its chirality. Calculated phonon modes at the zone center more or less accurately predicted the Raman active modes. The radial breathing mode is of particular interest as for a specific radius of a nanotube it is found to be independent of its chirality. We have also calculated the variation of RBM and G-band modes for tubes of different radii. RBM shows an inverse dependence on the radius of the tube. Finally, the values of specific heat are calculated for various nanotubes at room temperature and it was found that the specific heat shows an exponential dependence on the diameter of the tube.     

Application of shell model in molecular dynamics simulation to MgO

The P－V－T equation of state of MgO has been simulated under high pressure and elevated temperature using the molecular dynamics (MD) method with the breathing shell model (BSM). It is found that the MD simulation with BSM is very successful in reproducing accurately the measured molar volumes of MgO over a wide range of temperature and pressure. In addition, the MD simulation reproduces accurately the measured volume compression data of MgO up to 100GPa at 300K. It is demonstrated that the MD simulated P－V－T equation of state of MgO could be applied as a useful internal pressure calibration standard at elevated temperatures and high pressures.     

Theoretical investigations on vibrational properties and thermal conductivities of ternary antimonides TiXSb,ZrXSb and HfXSb (X = Si,Ge)

We have performed density functional calculations of the vibrational and thermodynamic properties of the ternary antimonides TiXSb, ZrXSb and HfXSb (X = Si, Ge). The direct method is used to calculate the phonon dispersion relation and phonon density of states for these compounds as well as their infrared and Raman active mode frequencies for the first time. Their dynamical stability is confirmed by phonon spectra. The lattice thermal conductivities of these compounds have been calculated from third-order force constants and plotted as a function of temperature. We have also evaluated the high temperature thermal conductivity by means of the Clarke’s model and Cahill’s model. Some selected thermodynamical properties, e.g. Gibbs free energy, entropy and heat capacity at constant volume are predicted theoretically and discussed. We have showed the relationships between thermodynamical properties and temperature.     

Hot-electron drift velocity in III–V semiconductors under the condition of impact ionization

A calculation has been carried out for the drift velocity of electrons in the highfield region under the condition of impact ionization in III–V semiconductor compounds.The energy-balance equation of the one-electron model has been solved considering alloy scattering and carrier-carrier interaction, in addition to optical phonon and ionization scattering. Fairly good agreement is obtained for GaAs with the available experimental and Monte-Carlo results. Graphs for the high-field drift velocity has also been plotted for Ga_1–x In_xAs (x = 0.53) at different ratios of ionization mean-free path and optical phonon mean-free path. The plot of high-field drift velocity versus ionization rate reveals that the high-field drift velocity strongly depends on the ionization rate of carriers, and vice versa.     

First-principles calculation of structural stability,lattice dynamic and thermodynamic properties of BeX (X = S,Se and Te) compounds under high pressure

The phase transitions, lattice dynamical and thermodynamic properties of BeS, BsSe and BeTe at high pressure have been investigated with the density functional theory. The calculated equilibrium structural parameters agree well with the available experimental and theoretical values. The phase transition pressures from the zinc-blende (ZB) to the nickel arsenide (NiAs) phase of these compounds are determined. The calculated phonon dispersion curves of these compounds in ZB phase at zero pressure do not show any anomaly or instability. Dynamically, the ZB phase of BeS, BeSe and BeTe is found to be stable near transition pressures P_T. Within the quasiharmonic approximation, the thermodynamic properties including the thermal expansion coefficient, heat capacity at constant volume, heat capacity at constant pressure and entropy are predicted.     

Lattice vibrational properties of TmTe

We have investigated the lattice dynamical properties of a TmTe compound by using a breathing shell model suitable for this compound. The calculated phonon dispersion curves (PDC) reveal that this compound does not show any anomaly in their phonon properties. Our results on PDC, phonon density of states and lattice specific heat reveal that the phonon properties of this compound are like the other rare earth chalcogenides, particularly Eu-chalcogenides. We emphasize the need of measurements of the complete PDC of TmTe to support the present results on the calculated phonon properties.     

A symmetry-adapted force-constant lattice-dynamical model for single-walled carbon nanotubes

We develop a lattice-dynamical model based on the screw symmetry of single-walled carbon nanotubes that allows for reducing the size of the dynamical matrix to six, for all tube chiralities. The model uses force constants derived from fitting to the phonon dispersion of 2D graphite. We present the calculation procedure in a clear and transparent way, making the model easier to follow. We calculate the phonon dispersions of a number of nanotubes of different chiralities. The splitting of two highest Raman active modes and the radial breathing mode frequency are studied by changing the tube diameter and chirality.     

Quantitative investigation of thermal phonon pulses in sapphire,silicon, and quartz

Using pulse-heated constantan films as a thermal phonon radiator and superconducting tin bolometer as a phonon detector, we present for the first time a full quantitative comparison between observed bolometer signals and adequate rigorous model calculations for transmission experiments ina-cut sapphire, [111]-cut silicon, as well asX-cut quartz andZ-cut quartz. Details of the observed phonon signals are explained and understood. From these experiments, we are also able to extract information about the phonon absorption coefficient in the normal state of the polycrystalline tin bolometer for longitudinal and transverse polarized phonons in quantitative agreement with an earlier experiment ina-cut sapphire which was performed with a superconducting tunnel junction as a detector. The observed transmission signals can be explained for sapphire and silicon by ballistic propagation with additional small angle scattering, but for quartz strong frequency downconversion occurs for phonons with frequencies above half a Terahertz.In a succeding paper (Part II) the parameter deduced from the transmission experiment are applied to the analysis of the observed phonon signals in reflection experiments in the same crystals under the same conditions.Supported by Deutsche Forschungsgemeinschaft     

Lattice dynamical study of body-centred tetragonal indium

The phonon dispersion curves, phonon frequency distribution function as well as the lattice specific heat of body-centred tetragonal indium have been deduced using a lattice dynamical model which includes central, angular and volume forces. Six elastic constants, four zone boundary frequencies and an equilibrium condition were used in the evaluation of the force constants. It is shown that this model is elastically consistent and satisfies the symmetry requirements of the lattice, the phonon frequencies of indium deduced from it are in very good agreement with the experimental values of Reichardt and Smith and the theoretical values of Garrett and Swihart, and theθ _D values compare well with the experimental values over a wide temperature range. The apparent discrepancies in the phonon dispersion curves and theθ _D-T curves obtained from deficient models, importance of umklapp processes and the significance of angular forces in the lattice dynamical models are discussed.     

Phonon scattering at siliconcrystal surfaces

Our observations of the reflection or backscattering of high-frequency phonons (v =280 GHz to 1 THz) at silicon-solid interfaces disagree significantly with predictions from the acoustic mismatch model. Interfaces composed of materials theoretically wellmatched, show high scattering experimentally. In contrast, interfaces theoretically poorly matched, show less phonon scattering than expected. Generally, this is best expressed by the fact that the interface scattering ranges from roughly 30–60% for different phonon modes with little dependence on the material covering the silicon crystal and different techniques of interface preparations. Thus, our experiments indicate that the well-known Kapitza anomaly of the phonon scattering at solid-liquid helium interfaces is not a special case; the same anomaly appears to be present at all tested interfaces. Our experiments are compared with detailed calculations which either assume pure specular or pure diffusive scattering. In these calculations the influence of the crystal anisotropy for the phonon propagation (phonon focussing) is included. This comparison shows, especially for the free silicon surface, that phonons are completely diffuse scattered. Hence, the acoustic mismatched model relying on specular reflection cannot be applied to the real silicon interface. The frequency dependence of phonon scattering at a free silicon interface indicates the existence of at least two different diffusive scattering mechanisms. Within our experimental limits in these two scattering processes the phonons are elastically scattered.     

Static and dynamic properties of KCN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Cl<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>

An extended three-body force shell model (ETSM) has been applied to investigate the static and dynamic properties of KCN _x Cl_1−x for the compositionx = 0.56 and 1.0 at 300 K. The phonon dispersion curves computed by us are compared with the single crystal neutron diffraction data. The unusual features of these curves are the upward curvature seen in some of the acoustic branches. This is a result ofK-dependent softening of the phonon due to translation-rotation coupling. The transverse acoustic branch is more soft near the zone centre.