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.     

First-principles study of lattice dynamics and thermodynamics ofosmium under pressure

We have performed the first-principles linear response calculations of the lattice dynamics, thermal equation of state and thermodynamical properties of hcp Os metal by using the plane-wave pseudopotential method. The thermodynamical properties are deduced from the calculated Helmholtz free energy by taking into account the electronic contribution and lattice vibrational contribution. The phonon frequencies at Gamma point are consistent with experimental values and the dispersion curves at various pressures have been determined. The calculated volume, bulk modulus and their pressure derivatives as a function of temperature are in excellent agreement with the experimental results. The calculated specific heat indicates that the electronic contribution is important not only at very low temperatures but also at high temperatures due to the electronic thermal excitation. The calculated Debye temperature at a very low temperature is in good agreement with experimental values and drops to a constant until 100~K.     

Surface phonons of LaB6(100): deformation of boron octahedra at the surface

The surface phonon dispersion of clean LaB₆(100) surface has been measured by means of high resolution electron energy loss spectroscopy. Eight vibrational modes, of which most are located in the energy gaps between the bulk phonon bands, have been detected. The lattice dynamical calculation of a slab-shaped crystal based on a force constant model has reproduced these experimental dispersion curves, which indicates the large increase in the force constant of interoctahedral boron-boron bond at the surface by 25%, and the large decrease in the force constants of intraoctahedral boron-boron bonds at the surface by 25–50%. These changes together with the analysis of the bulk phonon structure of metal hexaborides strongly suggest that the boron octahedra at the surface are expanded by about 0.004 nm parallel to the surface.     

Lattice-dynamical functions of solids at very high pressures

Abstract

Vibrational spectra of face-centered cubical (f.c.c.) solids are investigated at the pressure region, where the quantum-statistical model for the electron energy is applicable. Phonon dispersion curves are obtained for different values of the specific volume. The integration of the phonon spectra over the Brillouin zone yields the zero-point vibrational energy, the Debye temperature, the Gruneisen coefficient, mean-square amplitude of zero-point and thermal vibration, the melting temperature. All quantities under consideration are calculated from the universal functions of the reduced volume, using the scaling relations for given atomic number 2.     

Surface plasmons in a free-electron metal

The dispersion and damping of the surface plasmons are calculated for a free-electron model of Al. At large wave-vector the frequency of the surface plasmons approaches that of the bulk plasmons. Their damping remains quite small up to a wave-vector close to the bulk plasmon cut-off. The change in zero-point energy of the plasmons is calculated, and it gives a large positive contribution to the surface energy.     

Surface cation ratios of binary oxide solid solutions

The cation ratios in the (100) surface of cubic oxides of bulk composition A_0.99B_0.01O, in which A and B are divalent cations were calculated using a monolayer model. Divalent cations including Ni, Co, Mn, Fe and Mg were studied. The cations were represented by a shell model, and the surface compositions were calculated by minimizing the total Gibbs free energy of the solid. The bulk energy change on surface segregation was evaluated by minimizing the energy change on substituting one bulk cation by another in an infinitely dilute solid solution and the surface energy was evaluated by a statistical method to accommodate the possibility that both cations can exist at non-negligible densities at the surface. The bulk energy change on surface segregation was found to be dominant in most cases. The surface energy change, the entropy change, and the change in crystal field stabilization energy were all secondary. Thus, except when the difference in ionic radii is very small, the larger cation is always more preferred at the surface. This conclusion appears to be in agreement with available experimental data.     

Ab initio lattice dynamics and piezoelectric properties of MgS and MgSe alkaline earth chalcogenides

We have studied structural, elastic, dielectric, vibrational, and piezoelectric properties of rock-salt and zinc-blende Mg alkaline earth chalcogenides (MgS, and MgSe) by using the plane-wave pseudopotential method within the local density approximation. The calculated lattice constant, bulk modulus, and elastic constants for these compounds are found to be in good agreement with experiment. The density functional perturbation theory has been employed to derive the Born effective charge and high-frequency dielectric constant and to calculate phonon dispersion curves and density of states. The piezoelectric constant has also been determined. The calculated results are compared with theory and experiment when available and showed reasonable agreement. In other cases, our results are predictions. The pressure dependence of the studied quantities has been examined and discussed. The pressure coefficients and mode Grüneisen parameters are determined.     

金属铍热力学性质的理论研究

使用第一性原理方法结合平均场模型研究了压力从0到150GPa、温度从0到1500K，金属铍六角密排结构(hcp)的热力学性质，包括铍的常态性质，等温高压物态方程，以及常压下平衡体积、体弹模量随温度的变化，Hugoniot曲线等.0K物态方程由广义梯度近似下的密度泛函理论计算，粒子热运动的贡献由平均场模型计算.由于铍的Debye温度比较高，计算自由能时考虑了零点振动能修正.计算结果与已有的静力学和冲击波实验数据符合得非常好. 关键词： 热力学性质 物态方程 第一原理计算     

CH_4和CD_4解离吸附的量子含时动力学研究

运用含时波包法 (time -dependentwavepacketmethod) ,对CH4和CD4在光滑静止的Ni( 10 0 )表面的解离吸附进行了量子动力学研究与计算。不同振动态下解离几率随平动能的变化曲线表明 ,反应分子的振动能对分子的解离有重要贡献 ,其反应趋势 ,与其它理论模型得到的结果一致。CH4与CD4解离几率的对数随平动能的变化曲线表明 ,CH4的解离几率比CD4的要高得多 ,这种同位素效应 ,是由它们不同的零点能和量子隧道效应引起的 ,且与实验结果符合得比较好     

CH4和CD4解离吸附的量子含时动力学研究

运用含时波包法(time-dependent wave packet method),对CH4和CD4在光滑静止的Ni(100)表面的解离吸附进行了量子动力学研究与计算.不同振动态下解离几率随平动能的变化曲线表明,反应分子的振动能对分子的解离有重要贡献,其反应趋势,与其它理论模型得到的结果一致.CH4与CD4解离几率的对数随平动能的变化曲线表明,CH4的解离几率比CD4的要高得多,这种同位素效应,是由它们不同的零点能和量子隧道效应引起的,且与实验结果符合得比较好.     

Ab initio calculation of elastic properties of rock-salt and zinc-blend MgS under pressure

The elastic properties of zinc-blend (ZB) and rock-salt (RS) MgS are calculated by ab initio method. The calculation shows that the enthalpy for RS structure and for ZB structure essentially is the same at ambient pressure. The ZB structure becomes unstable above 5 GPa. For these two structures, the pressure dependences of typical elastic properties, i.e. the bulk modulus, the shear modulus, the Young's modulus, the Poisson's ratio, and the anisotropy factor, are presented. The Debye temperature and sound velocity under high pressure have also been calculated. Debye approximation is used to estimate the zero-point vibrational energy.     

Dynamical stability and phase transition of ZrC under pressure

A comprehensive first principles study of structural, elastic, electronic, and phonon properties of zirconium carbide (ZrC) is reported within the density functional theory scheme. The aim is to primarily focus on the vibrational properties of this transition metal carbide to understand the mechanism of phase transition. The ground state properties such as lattice constant, elastic constants, bulk modulus, shear modulus, electronic band structure, and phonon dispersion curves (PDC) of ZrC in rock-salt (RS) and high-pressure CsCl structures are determined. The pressure-dependent PDCs are also reported in NaCl phase. The phonon modes become softer and finally attain imaginary frequency with the increase of pressure. The lattice degree of freedom is used to explain the phase transition. Static calculations predict the RS to CsCl phase transition to occur at 308?GPa at 0?K. Dynamical calculations lower this pressure by about 40?GPa. The phonon density of states, electron–phonon interaction coefficient, and Eliashberg's function are also presented. The calculated electron–phonon coupling constant λ and superconducting transition temperature agree reasonably well with the available experimental data.     

First-principles lattice dynamical study of ScAs and ScSb at zero and high pressure

A first-principles pseudopotential method is used to investigate the structural and elastic properties of ScAs and ScSb in their ambient B1(NaCl) and in high pressure B2 (CsCl) phases and phonon structures at zero and close to phase transition pressure. The calculated lattice constants, static bulk modulus, first order pressure derivative of the bulk modulus and the elastic constants are reported in B1 and B2 structures and compared with available experimental and other theoretical results. The phonon properties of these two compounds are compared among themselves which reveal that these compounds are predominantly metallic, due to degeneracy of optical frequencies at the zone centre. At high pressure, near the B1 to B2 transition, the LA mode at X-point softens leading to structural instability.     

Direct observation of the mass renormalization in SrVO3 by angle resolved photoemission spectroscopy

Band dispersions and Fermi surfaces of the three-dimensional Mott-Hubbard system SrVO3 are directly observed by angle-resolved photoemission spectroscopy. An observed spectral weight distribution near the Fermi level (E(F)) shows cylindrical Fermi surfaces as predicted by band-structure calculations. By comparing the experimental results with calculated surface electronic structures, we conclude that the obtained band dispersion reflects the bulk electronic structure. The enhanced effective electron mass obtained from the energy band near E(F) is consistent with the bulk thermodynamic properties and hence with the normal Fermi-liquid behavior of SrVO3.     

The zero-point energy in the molecular hydrogen crystal

We propose a modified Einstein approximation to describe zero-point energy vibrations in a quantum crystal. Our aim was to develop a computationally cheap tool suitable for lattice structure optimisation. As in the classical Einstein model the representative atom vibrates in an effective potential due to the surrounding atoms of the crystal; the atoms however are not strictly placed at the positions corresponding to the crystal potential energy minima but their positions are described by the quantum mechanical density distributions. The effective potential computed that way is suitable for the application in solid para-hydrogen in contrast to the normal (unmodified) Einstein approximation. We compute the cohesive energy of the para-hydrogen crystal and perform lattice structure optimisation. The hexagonal closed packed is more stable than the fcc closed packed lattice and the lattice constants obtained are in very good agreement with the experimental values.     

Magnetic field dependence of vibrational excitations in a two-dimensional triangular Wigner crystal

It is shown that a static magnetic field applied perpendicular to a quasi twodimensional Wigner crystal lifts the degeneracy, e.g., of transverse and longitudinal vibrational frequencies and modifies their dispersion. The dependence of the effect on the magnitude of the applied field, on the electron surface concentration, and its relevance for observing a two-dimensional Wigner crystal are investigated quantitatively for a triangular lattice of a three-layer structure in harmonic approximation.     

Potential energy of an isolated gold atom on the (100) surface of alkali halide crystals

The energy of an isolated gold atom on the (100) surface of several alkali halide crystals (NaCl, NaF, KCl, KBr) is calculated as a function of distance above the crystal surface. The calculations include dispersion, electrostatic and repulsive potentials and are performed by direct summation over near neighbours and integration over the rest of the crystal. Detailed potential maps of the (100) surface as seen by a gold adatom are obtained, preferred adsorption sites are identified, and surface quantities such as adsorption energies, minimum energy barriers for diffusion and vibrational frequencies are computed. The effects of relaxations of the (100) surface ions due to both the presence of the surface and the presence of the adatom are examined. Both are found to be significant. Some comparison with experimental results is made.     

Determination of a Potential Energy Surface for CO2 Using Generalized Internal Vibrational Coordinates

A potential energy surface for CO2 is determined from experimental data using generalized internal vibrational coordinates. These coordinates are defined as two arbitrary distances and the angle between them and depend on two external parameters, which can be properly optimized. An optimal generalized internal coordinate system is obtained for CO2 by minimizing unconverged vibrational energies with respect to the external parameters. The optimal coordinates are shown to be superior to previously derived normal hyperspherical coordinates for this molecule. A nonlinear least-squares fit of the potential energy surface of CO2 to observed vibrational frequencies is made by using the optimal internal coordinates and fully variational calculations. The potential function is represented by a fourth-order Morse-cosine expansion and its quality is checked by computing highly excited vibrational transition frequencies which were not included in the fit. Copyright 1999 Academic Press.     

Ab initio total energy calculation of the dynamical stability of noble metal carbides

The structural, electronic, vibrational and thermodynamical properties of transition metal carbides RuC, RhC, PdC and AgC are investigated using the plane-wave pseudopotentials method within the generalized gradient approximation (GGA) in the frame of density functional theory (DFT). There is a good agreement between present theoretical and available experimental theoretical data in the case of ground state properties such as lattice parameter and bulk modulus. The electronic band structure of these compounds show that all compounds except RuC in zinc blende phase are metallic in nature. RuC in zinc blende phase is semiconducting in nature with an indirect band gap. The phonon properties of RhC, PdC and AgC are investigated for the first time. The phonon frequencies in the phonon dispersion curves are positive throughout the Brillouin zone for zinc blende RuC and AgC and rocksalt RhC and PdC indicating dynamical stability for these compounds in the said phases. Temperature variation of thermodynamical properties for noble metal carbides are calculated and discussed.     

Vibrational and thermodynamic properties of metals from a model embedded-atom potential

This work provides the first systematic test of validity of the embedded-atom potentials of Mei et al. [Phys. Rev. B 43 (1991) 4653], via a complete study of the vibrational and thermodynamic properties of isoelectronic transition (Ni, Pd, Pt) and noble (Cu, Ag, Au) metals. Phonon dispersion curves and thermal properties are studied within the quasiharmonic approximation. Results for the temperature-dependence of the lattice constants, coefficients of linear thermal expansion, isothermal and adiabatic bulk moduli, heat capacities at constant volume and constant pressure, Debye temperatures and Grüneisen parameters are presented. Electronic contribution to the specific heat is included explicitly via density-functional calculation. The calculated phonon frequencies for Ag and Cu agree well with the results from inelastic neutron scattering experiments. Despite less satisfactory agreement between calculated and measured phonon frequencies for the other four metals, isothermal and adiabatic bulk moduli and the specific heats of all metals are reproduced reasonably well by the model, while the Grüneisen parameter and Debye temperature are underestimated by about 10%. The coefficient of linear thermal expansion is underestimated with respect to measured values in most cases except for Pt and Au. The results are good for Pt up to 1000 K and for Au up to 500 K.