Structural stability of intermetallic compound YCu studied by ab initio total energy calculation

High pressure effect on the structural polymorphy of YCu was studied based on the first principle density functional theory. The calculated values of lattice parameters are in good agreement with the available experimental results. The geometry optimization results indicate the anisotropy of the compressibility of FeB-type YCu under high pressure. It is remarkable that the compressibilities along the b- and c-axes experience an abnormality at about 3.3 GPa. Energy calculation results demonstrate that YCu is stable in the FeB-type structure at low temperature and ambient pressure, which is in good agreement with the experimental results. And there exists a structural phase transition from FeB-type structure to CsCl-type structure at the transition pressure of approximate 6.7 GPa. This is the quantitative theoretical prediction of structural phase transition, and it still awaits the experimental confirmation.     

Partial molar adiabatic compressibilities of transfer of some amino acids from water to aqueous lactose solutions at different temperatures

Apparent molar adiabatic compressibilities (K_{?, s}) of glycine, L-alanine, L-valine, and L-leucine have been determined in aqueous and mixed aqueous solutions of lactose (2 to 6 mass%) at T = (293.15, 298.15, 303.15, and 308.15) K. From these data partial molar adiabatic compressibilities at infinite dilution (K_{?, s}⁰) have been evaluated to calculate corresponding transfer function. The transfer partial molar adiabatic compressibilities at infinite dilution (ΔK_{?, s}⁰) are found to be positive. The decrease in the magnitude of transfer partial molar adiabatic compressibilities from glycine to L-leucine indicates the dominance of hydrophobic-hydrophobic interactions between the increasing side chains of amino acids. Also, the contributions of NH₃⁺COO⁻ , and CH₂ groups have been calculated by the linear correlation of K_{?, s}⁰ with number of carbon atoms in the alkyl chain of amino acids.     

The absolute thermoelectric power of polyvalent liquid metals

Results on the measurement of the absolute thermoelectric power of ten polyvalent liquid metals (Al, Bi, Cd, Ga, Hg, In, Pb, Sn, Tl, Zn) from their melting points to about 750°C are reported. The electrical resistivities and the absolute thermoelectric powers of these metals have been calculated using the latest available data on structure factor and Harrison and Animalu form factors. These are compared with the experimental values. It is seen that whereas the predicted and experimental values of the electrical resistivities are in reasonable agreement, those for the absolute thermoelectric power are not. It is suggested that the experimental data on the absolute thermoelectric powers and the resistivities of liquid metals may be used to find the magnitude of the form factor at K = 2k _F.     

Application of a structure factor-potential relationship to the electrical resistivity of the liquid alkali metals

In the Ziman formulation for the electrical properties of liquid metals, the resistivity depends on an average of the product of the structure factor and the pseudopotential. Ascarelli, Harrison and Paskin have derived a relationship for small wave vector between the structure factor and the pseudopotential for liquid metals such as the alkali metals. This formulation has been used over the entire range of wave vector (k = 0 to 2k _F). The resistivities of Na, K, Rb and Cs calculated with no adjustable parameters are within 25% of the observed values, while Li is underestimated by about a factor of five. The temperature dependencies of all but Li (which is anomalously non-linear) are in similar agreement with experiments made at constant volume.     

The volume dependent total energy of metals and the ionic radii

The cohesive energies, lattice constants and compressibilities for a number of metals are correlated with the ionic radii through second order pseudo-potential theory. The model yields reasonable results not only for simple metals of arbitrary valency, but for transition elements with no more than 5 d-electrons.     

Zero frequency dynamical structure factor of liquids

Expressions for the zero frequency dynamical structure factor, S(k, ω = 0), are derived from the theory of collective motion of liquids proposed by the authors and that by Hubbard and Beeby. Calculations on liquid argon show that in comparison with the latter, the former theory gives much higher values of S(k, 0) which are in good agreement with the recent experimental results.     

Densities, speeds of sound and viscosities of binary liquid mixtures of octan-2-ol with benzene and halobenzenes at 298.15 and 303.15 K

Densities ρ, speeds of sound u, viscosities η and refractive indices n_D of binary mixtures of octan-2-ol with benzene, chlorobenzene and bromobenzene have been measured over the entire range of composition at 298.15 and 303.15 K and atmospheric pressure. From the experimental data, excess molar volumes V^E, isentropic compressibilities κ_S, excess isentropic compressibilities κ_S^E, and deviations of speeds of sound u^D, have been calculated at 298.15 and 303.15 K. These excess functions have been fitted to the Redlich-Kister polynomial equation. The viscosity data have been correlated using Kendall-Monroe, Grunberg-Nissan, Tamura-Kurata, Hind-Mclaughlin Ubbelohde and Katti-Chaudhary viscosity models, and McAllister's three-body interaction model at different temperatures.     

Lattice mechanical properties of alkaline earth metals in bcc and fcc phases

A model pseudopotential depending on an effective core radius treated as a parameter is used for alkaline earth metals in bcc and fcc phases to study the Binding energy, Interatomic interactions, phonon dispersion curves, Phonon density of states, Debye-Waller factor, mean square displacement, Debye-Waller temperature parameters, dynamical elastic constants (C₁₁, C₁₂ and C₄₄), bulk modulus (B), shear modulus (C′), deviation from Cauchy relation (C₁₂−C₄₄), Poisson's ratio (σ), Young's modulus (Y), behavior of phonon frequencies in the elastic limit independent of the direction (Y₁), limiting value in the [1 1 0] direction (Y₂), degree of elastic anisotropy (A) and propagation velocities of the elastic waves. The contribution of s-like electrons is incorporated through the second-order perturbation theory due to model potential. The theoretical results are compared with the existing experimental data. A good agreement between theoretical investigations and experimental findings has confirmed the ability of our potential to yield large numbers of lattice mechanical properties of certain alkaline earth metals.     

Surface energy of liquid metals at the melting temperature related to bulk liquid structure

The product σχ_Tm of surface energy σ and isothermal compressibility σχ_Tm for liquid metals at the melting temperature T_m yields a length l ranging from about 0.2 to 0.5 Å over the entire range of liquid metals. The variation of l, which has been related brfore to the thickness of the liquid-vapour interface, is shown to be accurately represented by , where the constant c is determined empirically, K_B and N being the Boltzmann factor and Avogadro's number respectively, and S_Tm(0) the bulk liquid structure factor in the long wavelength limit at the melting temperature. A microscopic interpretation of l is proposed.     

Thermoelastic and thermodynamic properties of harzburgite—An upper mantle rock

A number of thermoelastic and thermodynamic properties such as compressibilities, specific heat ratio, specific heat capacities, Grüneisen parameters, Debye temperature, the melting temperature, and their dependence on temperature and pressure have been obtained for the harzburgite rock of Oman ophiolite suite. Debye temperature Θ_D and the ratio of the specific heats are the basic inputs which are determined here by making use of the seismic velocities and the density data. The specific heat capacities C_P and C_V are evaluated from the thermodynamic equations as well as from the Debye theory. These data along with the computed values of compressibilities have been used to evaluate the Grüneisen parameter and its dependence on temperature through thermodynamic and acoustic relations. The computed values of the Debye temperature has also been found very helpful to estimate the melting temperature of the rock whose pressure dependence is analyzed following the Clausius-Clapeyron equation.     

Torsional barrier and equilibrium structure of ethyl cyanide

The quadratic, cubic and semi-diagonal quartic force field of ethyl cyanide has been calculated at the B3LYP level of theory employing a basis set of triple-ζ quality. A semi-experimental equilibrium structure has been derived from experimental ground state rotational constants and rovibrational interaction parameters calculated from the ab initio force field. This structure is in excellent agreement with the ab initio structure calculated at the CCSD(T) level of theory using a basis set of quadruple-ζ quality and a core correlation correction. The empirical structures are also determined and their accuracy is discussed. The potential barrier V₃ hindering internal rotation of the methyl group has been calculated from 23 rotational transitions of CH₃CH₂C¹⁵N which were found split into doublets, giving V₃ = 3074(27) cal mol⁻¹.     

Coexistence of ferro- and antiferromagnetism — A spin fluctuation theory

The coexistence of and transition between ferro- and antiferromagnetism in itinerant electron system are investigated by extending the spin fluctuation theory of ferromagnetic metals by Usami and Moriya. Calculation is made on a model density of states, which simulates the one for d metals with a body centered cubic crystal structure. The result shows that the wavevector-dependent susceptibility χ_q has a two peaks at q = 0 and q = Q for the suitable choice of parameters and the coexistence is realized when the amplitude of spin fluctuation takes a proper value. Paramagnetic susceptibility of this system is also discussed.     

A relation between structure and pair potential for liquid metals

We emphasize the importance of considering the relationship between the structure of a liquid and the interatomic potential directly from the point of view of wave vector space (k space). Although the Ornstein-Zernike equation was not originally derived from this point of view, this equation when transformed into the k-space representation has direct physical content, when coupled with a normal mode representation according to the approaches of Pines and Bohm (1952), and Percus and Yevick (1958). These normal modes are defined isothermally, and the relation to the dynamical modes of the liquid is discussed. The use of a simple k-space relationship between the transform of the Ornstein-Zernike direct correlation function and the transform, V_k , of the interatomic potential is explored. This leads to a correspondingly simple relationship between the structure factor and the interatomic potential. It is equivalent to a generalized Debye-Hückel equation and is expected to be valid only under special circumstances; namely, where the potential is long range in a particular sense and the small k behaviour of V_k is dependent mainly upon this long-range behaviour and relatively insensitive to details of the potential at short distances. It is noted that these conditions appear to be met reasonably well for the liquid alkali metals. The comparison of theory and experiment is somewhat uncertain because of incomplete experimental data on the structure factor as well as unresolved theoretical issues.     

On the initial stage of spinodal decomposition

A consistent theory describing the initial stage of spinodal decomposition of a two-component system is proposed. It is shown that the structure factor S(q, t) has two maxima as a function of wavenumber at this stage. The main maximum point q₊ varies with time, first moving from q_saddle to q_m (given by expressions (22) and (12), respectively) and then back after the turning point in time given by (26) is passed. The other maximum point is localized at q ≈ 0, and the corresponding peak amplitude is virtually independent of time. The characteristics of the main maximum are sensitive to the existence of the “zero” peak. Available experimental observations support the predictions of the theory.     

Ab initio anharmonic force field and equilibrium structure of carbonyl chlorofluoride

The quadratic, cubic, and semi-diagonal quartic force field of OCFCl has been calculated at the MP2 level of theory employing a basis set of triple-zeta quality. The spectroscopic constants derived from the force field are in excellent agreement with those from previous and new experiments. The equilibrium structure has been derived from experimental ground state rotational constants and ab initio rovibrational interaction parameters. This semi-experimental structure is in excellent agreement with the ab initio structure calculated at the CCSD(T) level of theory. This good agreement indicates that the derived structure is accurate. The equilibrium geometry is: r_e(CO)=1.173(1) Å; r_e(C-F)=1.323(1) Å; r_e(C-Cl)=1.721(1) Å; ∠_e(OCF)=124.0 (1)°; and ∠_e(OCCl)=126.4(1)°.     

The bulk modulus of SmFeAs(O0.93F0.07)

The crystal structure of SmFeAs(O_0.93F_0.07) has been investigated under high pressure (up to ∼9 GPa) by means of synchrotron powder diffraction analysis followed by Rietveld refinement. The bulk modulus was calculated (K₀ = 103 GPa) using a 3rd order Birch–Murnaghan equation of state and resulted in quite good agreement with theoretical calculations reported for LaFeAsO. The linear compressibilities β_a and β_c are 2.11(4) and 4.56(7) × 10⁻³ GPa⁻¹, respectively.     

无序晶态合金的电阻率

基于Baym原则,将Ziman型液态金属电阻理论推广到晶态金属及替代式的无序合金系统,给出了电阻率的一般表达式,讨论了它们的低温和高温行为。低温下用德拜晶格振动模型,无序晶态系统的电阻率可表为ρ=ρ₀+ρ_d(T/Θ)²+ρ_i(T/Θ)⁵,与实验一致。高温下,考虑到Debye-Waller因子及多声子效应,电阻率趋向饱和。用独立原子振动近似得到的简单公式与实验资料的比较表明:类似Nb这种电阻率的高温非线性偏离可以在本文的模型中自然地得到说明。