Lattice dynamics of BiFeO<Subscript>3</Subscript>: The untypical behavior of the ferroelectric instability under hydrostatic pressure

Within a nonempirical model of an ionic crystal with the inclusion of the dipole and quadrupole ion polarizations, the lattice vibrational frequencies, high-frequency dielectric constant, Born dynamic charges, and the elasticity moduli of the BiFeO₃ crystal have been calculated and their dependencies on the hydrostatic pressure in the cubic, rhombic, and rhombohedral phases have been determined. The results indicate the presence of the ferroelectric instability, which depends weakly on the pressure in all of the phases investigated. The dependence of the crystal lattice dynamics on the applied pressure for the cubic phases of BiAlO₃, BaTiO₃, and PbTiO₃ has been calculated for comparison.     

Crystal radii of ions in alkaline earth chalcogenides

The crystal radii of ions in alkaline earth chalcogenides have been calculated from the effective nuclear charges of isoelectronic ions. The ionic radii thus calculated are found to follow the polarizability—radius cubed relation, according to which the ratio of the electronic polarizability of an ion to the cube of its radius in the free state is nearly equal to that in the crystalline state. The interionic separations in alkaline earth chalcogenides and also AB₂ and A₂B type crystals obtained from the ionic radii reported in the present paper agree closely with the experimental values.     

Far-infrared optical properties of YVO4 single crystal

Near-normal incident infrared reflectivity spectra of a (001) YVO₄ single crystal have been measured at different temperatures in the frequency region between 100 and 6000 cm^-1. The reflectivity spectra are analyzed with the factorized form of the dielectric function, and the dielectric properties and optical conductivity of the YVO₄ crystal are obtained. From the TO/LO splitting, effective charges at different temperatures are calculated to study the ionicity of YVO₄. The internal modes of the VO₄^3- ion and the external modes of the Y(VO₄) lattice are compared with SiO₄^4- in zircon and with other rare-earth vanadates.     

Structural,elastic, electronic and optical properties of the cubic perovskites CaXO3 (X=Hf and Sn)

The structural, elastic, electronic and optical properties of CaXO₃ compounds with the cubic perovskites structure have been investigated, by employing a first principles method, using the plane wave pseudo potential calculations (PP-PW), based on the density functional theory (DFT), within the local density approximation (LDA). The elastic constants and their pressure dependence are calculated using the static finite strain technique. We derived the bulk, shear and Young’s moduli for ideal monocrystalline and for polycrystalline CaXO₃ aggregates which we have classified as ductile in nature. Band structures reveal that these compounds are indirect energy band gap (R-G) semiconductors; the analysis of the site and momentum projected densities, valence charge density bond length, bond population and Milliken charges, shows that bonding is of covalent–ionic nature. We have found that the elastic constants C₁₁, C₁₂, C₄₄ are in good correlation with the bonding properties. The optical constants, including the dielectric function, optical reflectivity, refractive index and electron energy loss, are calculated for radiation up to 20 eV.     

On the lattice dynamics of AgGaS2

Summary The vibrational spectrum and one-phonon density of states of a chalcopyrite crystal AgGaS₂ are calculated in an extended Keating’s model with two-bond-stretching and one-bond-bending force constants. Three charges of ions and three force constants are determined by a least-square fitting to experimental frequencies of long-wave phonons taken from Raman-scattering experiments. The calculated constant-volume specific heat, Debye temperature and elastic constants, of AgGaS₂ are in agreement with the experimental data of other authors.     

Lattice dynamics properties of XAs (X=Al,Ga and In) with zinc-blende structure from first-principle calculations

Band structures, density of states, dielectric and vibrational properties of XAs (X=Al, Ga and In) alloys with zinc-blende structure have been studied using the density functional theory (DFT). The calculated lattice constants, band gap, static dielectric constants and phonon frequencies are all in good agreement with the available experimental data and other theoretical results. The calculated results show that Born effective charges Z_B increase with cation mass. A similar tendency has been observed for phonon frequencies ω_TO and ω_LO. Calculation results prove that static dielectric constants ε(0) increase with atomic weight, i.e. in the sequences AlAs–GaAs–InAs, and show an inverse sequence for band gap.     

X-ray emission spectra and chemical bonding in TiC,TiN and TiO

The experimental X-ray emission spectra of titanium carbide, nitride and oxide have been obtained. Quantum-chemical calculations of the electronic structure of clusters in TiC, TiN and TiO have been carried out by the semiempirical Mulliken-Wolfsberg-Helmholtz method with self-consistency on charges and configurations. The results of these calculations are in good agreement with the X-ray spectroscopy data and offer a reasonable explanation of the experimental spectra. Chemical bonding and electronic structure of the compounds are discussed. Ionicity is shown to increase from TiC to TiO according to the electronegativity principle, the calculated charges on the metal ions being close to experimental estimates. The role of metal-metal and metal-nonmetal interactions in the chemical bonding is analysed. Vacancy models for TiO and their effect on the X-ray emission spectra are investigated. By the CNDO method with configurational interactions the optical spectrum of titanium carbide has been calculated. It is shown that this spectrum may be interpreted from the results for the [TiC₆] cluster, without introducing the Lye-Logothetis band scheme with negative charge on the metal ion.     

Some dynamical properties of a two-dimensional Wigner crystal

Results for the static part of the ground state energy of the square and hexagonal two-dimensional Wigner lattices are given. The hexagonal lattice has the lower energy. Phonon dispersion curves and the vibrational zeropoint energy are calculated for the hexagonal lattice. The dielectric susceptibility tensor of a two-dimensional Wigner crystal χ_αβ(q) has been determined in the long wavelength limit in the presence of a static magnetic field perpendicular to the crystal, and explicit expressions have been obtained for the hexagonal lattice. Applying the analysis developed by Chiu and Quinn, the results for the susceptibility have been used to obtain the dispersion relation for the plasma oscillations in the electron crystal on the assumption that the crystal is embedded in a dielectric medium. The dispersion curves have been calculated for differing magnitudes of the applied magnetic field.     

Electronic polarizabilities of ions in transition metal oxides

A method for evaluating the electronic polarizabilities from ionic radii in transition metal oxides has been suggested. The ionic radii used in the present calculations are those deduced from the electron density measurements. The calculated polarizabilities agree closely with the experimental values obtained from the electronic dielectric constant.     

Mechanical properties,Born effective charge tensors and high frequency dielectric constants of the eight phases of BaTiO<Subscript>3</Subscript>

We have preformed the first-principles calculations for the mechanical properties, Born effective charge tensors and high frequency dielectric constants of the eight phases of BaTiO₃. The independent elastic constants, bulk modulus, shear modulus, Young’s modulus and Poisson’s ratio were obtained, which were consistent with the available theoretical and experimental values. The mechanical stability and brittle/ductile behaviors of the eight phases of BaTiO₃ have been discussed. The calculated results indicated that the eight phases were all mechanically stable and behaved in a brittle manner. The calculated Born effective charge tensors shown the covalent Ti–O bond and ionic Ba–O bond. Moreover, the high frequency dielectric constants have been given.     

Electronic polarizabilities of ions in transition metal oxides

A method for evaluating the electronic polarizabilities from ionic radii in transition metal oxides has been suggested. The ionic radii used in the present calculations are those deduced from the electron density measurements. The calculated polarizabilities agree closely with the experimental values obtained from the electronic dielectric constant.     

Lattice dynamics and ferroelectric instability in ordered and disordered PbSc<Subscript>1/2</Subscript>Ta<Subscript>1/2</Subscript>O<Subscript>3</Subscript> and PbSc<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>O<Subscript>3</Subscript> solid solutions

The dynamic Born charges and the frequency spectra of lattice oscillations in the crystals of ordered and disordered PbSc_1/2Ta_1/2O₃ (PST) and PbSc_1/2Nb_1/2O₃ (PSN) solid solutions have been calculated within the framework of the generalized Gordon-Kim model with allowance for the dipole and quadrupole polarizabilities. The phonon spectra of both compounds contain ferroelectric soft modes. The influence of various interactions on the magnitude of dynamic charges and ferroelectric instability in PSN and PST solid solutions has been studied and it is shown that both these charges and the ferroelectric instability are determined by the competition between long-range dipole-dipole interactions and short-range dipole-charge interactions, the determining role played by the interaction of Nb (Ta) cations and oxygen anions in the Nb-O (Ta-O) bond direction.     

Electronic structure and optical properties of CdSexTe1−x mixed crystals

The band structure and optical properties of the CdSe_xTe_1−x ternary mixed crystals have been studied using the pseudopotential formalism under an improved virtual crystal approximation approach. Quantities such as, energy gaps, band-gap bowing parameters, electron effective mass and dielectric constants are calculated. Our results agree well with the available data in the literature. The composition dependence of all studied quantities has been expressed by quadratic polynomial forms.     

Hartree-Fock and density functional theory studies on ionization and fragmentation of halomethane molecules by positron impact

The fragmentation patterns of halomethane molecules CF₄, CCl₂F₂, CClF₃ and CHF₃ due to positron impact have been studied by using ab initio and density functional theory (DFT) methods. The geometries of parent molecules and fragments are optimized at HF, MP2 and B3LYP levels of theory using the 6–31+G(d, p) basis set. The calculated reaction energies agree with the experimental values. The condensed Fukui functions have been calculated using the atomic charges of the Mulliken population analysis (MPA) scheme for the halomethane molecules. The calculated condensed Fukui functions successfully predict the reactive site of the halomethane molecules for the positron, electron and radical attacks. The chemical hardness and chemical potential for the above molecules and its fragments are calculated.     

Ab initio vibrational and dielectric properties of chalcopyrite CuInS <Emphasis Type="Bold">2</Emphasis>

We have performed a first-principles study of structural, dynamical, and dielectric properties of the chalcopyrite semiconductor CuInS₂. The calculations have been carried out within the local density functional approximation using norm-conserving pseudopotentials and a plane-wave basis. Born effective charge tensors, dielectric permitivity tensors, the phonon frequencies at the Brillouin zone center and mode oscillator strengths are calculated using density functional perturbation theory. The calculated properties agree with infrared and Raman measurements. Received 12 December 2002 / Received in final form 17 March 2003 Published online 20 June 2003 RID="a" ID="a"e-mail: resul@ibu.edu.tr     

Ion velocity distribution function in intrinsic gas at cryogenic gas temperatures

The influence of elastic scattering on the ion distribution function in the plasma of an intrinsic gas in weak fields has been considered. An analytical expression valid for cryogenic temperatures of atoms has been obtained. The reduced He⁺–He, Ar⁺–Ar mobilities as functions of the temperature of atoms in a range of 4–1000 K have been calculated in the approximation of the zero field taking into account elastic collisions; the calculated dependences well agree with the available experimental data. It has been demonstrated that elastic collisions play an important role in the formation of the ion distribution function at low temperatures. The results of measurement of the ion mobility in the limit of the zero field at low temperatures can be used to obtain data on the ratio of elastic scattering and resonance charge exchange cross sections.     

a-Si:H中本征缺陷引起的赝隙态

本文取原子集团模型Si₈H₁₈,Si₁₇及从连续无规网络中挖取的集团模型Si₂₉和Si₄₇,用CNDO LCAO-MO方法计算其电子结构,探讨了a-Si:H中由弱键、弯键和带电组态等本征缺陷引起的赝隙态分布。结果表明,当弱键拉伸时,两个弱键态移动并收缩至带隙中央;过剩电荷使弱键能级移至价带顶或导带底附近;弯键态主要出现在价带顶附近。当弯键曲率较大时,弯键态上移至带隙中央以下的区域。结构拓扑无序导致 关键词：     

LiB3O5单晶的偏振喇曼散射谱

在室温下测量了LiB₃O₅单晶的各种振动类的偏振喇曼散射谱。利用因子群分析和变温测量等方法以及BO₃,BO₄基团振动谱带的结果,对振动模进行了初步指认。根据LO-TO劈裂的实验结果,计算出该晶体的静态介电系数和各极化模的有效电荷。 关键词：     

Infrared active phonon modes and ionicity of single crystal MgAl2O4

Near-normal incident infrared reflectivity spectra of （100） MgAl2O4 spinel single crystal have been measured at different temperatures in the frequency region between 50 and 6000 cm^-1. Eight infrared-active phonon modes are identified, which are fitted with the factorized form of the dielectric function. The dielectric property and optical conductivity of the MgAl2O4 crystal are analysed. From TO/LO splitting, the effective Szigeti charges and Born effective charges at different temperatures are calculated for studying the ionicity and the effect of polarization. Based on the relationship between the （LO-TO）1 splitting, which represents the transverse and longitudinal frequencies splitting of the highest energy phonon band in the reflectivity spectrum, and the ionic-covalent parameter, the four main phonon modes are assigned. MgA1204 can be considered as a pure ionic crystal and its optical characters do not change with decreasing temperature, so it may be used as a suitable substrate for high-Tc superconducting thin films.     

On the application of the theory of the brownian movement in a periodic potential to the study of inertial effects and dipole coupling

For a series of ten electron molecules (HF, H₂O, NH₃, CH₄) the molecular polarizability tensor and the derivatives with respect to the symmetry coordinates have been calculated from ab initio SCF wavefunctions using the finite field method as well as perturbation theory approaches. Raman intensities and degrees of depolarization derived from the finite field results agree well with the available experimental data.

The zeroth order bond polarizability model and the atom dipole interaction model have been analysed. Both models can be used to describe the computed static polarizabilities and the derivatives with respect to bond stretching, but fail for the derivatives with respect to the bending coordinates.