Ab initio calculations of structural,elastic and electronic properties of Li2O2

The equilibrium structure of the compound Li₂O₂ has been obtained via minimization of the total energy within the local density approximation (LDA) based on density functional theory (DFT). The calculated lattice parameters are in excellent agreement with available values. The elastic properties of Li₂O₂ are investigated. Values of all independent elastic constants (C ₁₁, C ₁₂, C ₁₃, C ₃₃ and C ₄₄) as well as bulk moduli in the a and c directions are predicted. Our calculated elastic properties suggest that the compound Li₂O₂ is slightly anisotropic but can be considered as an isotropic material compared with other highly anisotropic materials. The electronic properties, including the density of states and energy band structure, are obtained and we find that this compound behaves as a semiconductor.     

Phonon spectra of YTiO3 and Y2Ti2O7: Ab initio calculations

Using the Hartree-Fock and density-functional methods, we have calculated the structure and the lattice dynamics of YTiO₃. Frequencies of Raman and IR phonons of this crystal have been determined. The crystal structure and phonon spectrum of Y₂Ti₂O₇ have been calculated.     

Distribution of electric field gradients around impurities in aluminum

The electric field gradients caused by a vacancy, Mg, Ga, In, Si, Ge and Sn impurities at several near-neighbor sites in Al hosts have been calculated. The theory takes into account the contribution from the conduction electron screening cloud and the lattice strain caused by the impurities. The perturbed core as well as conduction electron densities around the impurities are calculated selfconsistently using the density functional theory. Assuming that the charge distribution around the impurity is spherically symmetric, an exact expression, valid at all distances, is derived for the conduction electron contribution to the electric field gradient. While this result is substantially different from those using the conventional asymptotic or pre-asymptotic expressions, it is found to be entirely inadequate in explaining the observed asymmetry and magnitude of the electric field gradient distribution in cubic metal alloys. The contribution due to the lattice strain is calculated using the point-ion model and a new analytic form for the elastic strain tensor. The combined strain and charge screening effect provides a satisfactory agreement between calculated and experimental electric field gradients. The difficulties standing in the way of an overall quantitative understanding of the electric field gradient in cubic metal alloys are discussed. The subsequent stages of improvement in both theory and experiment that can result in a better understanding of the problem are pointed out.     

外场下二甲基硅酮双自由基的从头计算研究

本文首先采用密度泛函(DFT)方法在6-311+g(2d,p)基组水平上计算研究了二甲基硅酮双自由基的红外振动光谱和核磁共振化学位移,而后在同样的基组水平上采用含时密度泛函(TDDFT)方法研究了外电场对二甲基硅酮双自由基的激发态、偶极矩和分子能量的影响,结果表明,不同方向的外加电场对他们的影响情况各不相同,沿X、Y方向的电场对激发态的激发能、振子强度影响在外加电场为0.005～0.010 a.u.是转折点,沿Z方向的电场在电场强度为0.015 a.u.是转折点.沿Y方向的外电场对分子的偶极矩、分子能量影响最大,沿X方向的外电场次之,沿Z方向的外电场对偶极矩和分子能量影响最小.     

Structural, elastic, vibrational and electronic properties of amorphous Al2O3 from ab initio calculations

First-principles molecular dynamics calculations of the structural, elastic, vibrational and electronic properties of amorphous Al(2)O(3), in a system consisting of a supercell of 80 atoms, are reported. A detailed analysis of the interatomic correlations allows us to conclude that the short-range order is mainly composed of AlO(4) tetrahedra, but, in contrast with previous results, also an important number of AlO(6) octahedra and AlO(5) units are present. The vibrational density of states presents two frequency bands, related to bond-bending and bond-stretching modes. It also shows other recognizable features present in similar amorphous oxides. We also present the calculation of elastic properties (bulk modulus and shear modulus). The calculated electronic structure of the material, including total and partial electronic density of states, charge distribution, electron localization function and the ionicity for each species, gives evidence of correlation between the ionicity and the coordination for each Al atom.     

Ab initio molecular dynamics in a finite homogeneous electric field

We treat homogeneous electric fields within density functional calculations with periodic boundary conditions. A nonlocal energy functional depending on the applied field is used within an ab initio molecular dynamics scheme. The reliability of the method is demonstrated in the case of bulk MgO for the Born effective charges, and the high- and low-frequency dielectric constants. We evaluate the static dielectric constant by performing a damped molecular dynamics in an electric field and avoiding the calculation of the dynamical matrix. Application of this method to vitreous silica shows good agreement with experiment and illustrates its potential for systems of large size.     

Ab initio calculations in a uniform magnetic field using periodic supercells

We present a formulation of ab initio electronic structure calculations in a finite magnetic field, which retains the simplicity and efficiency of techniques widely used in first principles molecular dynamics simulations, based on plane-wave basis sets and Fourier transforms. In addition we discuss results obtained with this method for the energy spectrum of interacting electrons in quantum wells, and for the electronic properties of dense fluid deuterium in a uniform magnetic field.     

First-principles calculations of electric field gradients of Sn compounds

The Discrete Variational (DV) LCAO Molecular Orbital method in the local density approximation was employed to obtain the electronic structure of clusters representing three compounds of Sn(II), namely SnF₂, SnO and SnS and two of Sn(IV): SnF₄ and SnO₂. The electric field gradients at the Sn nucleus were calculated and a value for the nuclear quadrupole moment Q was determined.     

First-principles calculation of electric field gradients and hyperfine couplings in YBa2Cu3O7

The local electronic structure of YBa₂Cu₃O₇ has been calculated using first-principles cluster methods. Several clusters embedded in an appropriate background potential have been investigated. The electric field gradients at the copper and oxygen sites are determined and compared to previous theoretical calculations and experiments. Spin polarized calculations with different spin multiplicities have enabled a detailed study of the spin density distribution to be made and a simultaneous determination of magnetic hyperfine coupling parameters. The contributions from on-site and transferred hyperfine fields have been disentangled with the conclusion that the transferred spin densities essentially are due to nearest neighbour copper ions only with marginal influence of ions further away. This implies that the variant temperature dependencies of the planar copper and oxygen NMR spin-lattice relaxation rates are only compatible with commensurate antiferromagnetic correlations. The theoretical hyperfine parameters are compared with those derived from experimental data. Received 10 April 2001 and Received in final form 19 June 2001     

Nonempirical cluster calculations of the electric field gradient tensor in yttrium-aluminum garnet Y3Al5O12

The electric field gradient (EFG) tensor at the aluminum nucleus sites in yttrium-aluminum garnet Y₃Al₅O₁₂ is calculated using the Hartree-Fock method and the nonempirical cluster approach. It is shown that the EFG tensor at the Al_tetr sites is described well taking into account the nearest neighbors (an [AlO₄]^?5 cluster), whereas for the Al_oct sites the effect of more distant ions is important. The results are compared with the available experimental data and the results of band calculations.     

Ab initio cluster calculations of Co3+ spin states in RBaCo2O5.5 (R=Ho, Gd)

Two types of oxygen-deficient perovskites RBaCo₂O_5.5(R=Ho,Gd) related to the “122” type structure (a _p × 2a _p × 2a _p ) have been studied on the basis of ab initio cluster calculations. We consider the peculiar behavior of the trivalent ions Co³⁺(3d ⁶) in either octahedral or pyramidal oxygen coordinations, which is related to a structural first-order phase transition in both compounds. Relative energy positions of low spin (LS, S = 0), intermediate spin (IS, S = 1) and high spin (HS, S = 2) electron configurations are calculated for the low-and high-temperature lattice structures of RBaCo₂O_5.5. A combined analysis of the calculated results and experimental structural data leads to a simple model that captures the most prominent features of the phase transition common to both compounds.     

Ab initio theory and calculations of X-ray spectra

There has been dramatic progress in recent years both in the calculation and interpretation of various x-ray spectroscopies. However, current theoretical calculations often use a number of simplified models to account for many-body effects, in lieu of first principles calculations. In an effort to overcome these limitations we describe in this article a number of recent advances in theory and in theoretical codes which offer the prospect of parameter free calculations that include the dominant many-body effects. These advances are based on ab initio calculations of the dielectric and vibrational response of a system. Calculations of the dielectric function over a broad spectrum yield system dependent self-energies and mean-free paths, as well as intrinsic losses due to multi-electron excitations. Calculations of the dynamical matrix yield vibrational damping in terms of multiple-scattering Debye–Waller factors. Our ab initio methods for determining these many-body effects have led to new, improved, and broadly applicable x-ray and electron spectroscopy codes. To cite this article: J.J. Rehr et al., C. R. Physique 10 (2009).     

Ab initio calculations of the vibrational spectra of AgInSe2 and AgInTe2

The phonon spectra and densities of states of AgInSe₂ and AgInTe₂ semiconductor crystals with a chalcopyrite structure have been calculated from first principles by the linear response method. The frequencies calculated at the center of the Brillouin zone are in agreement with the experimental data obtained using IR and Raman spectroscopy. According to the atomic contributions to the vibrational modes, the spectra of the AgInSe₂ and AgInTe₂ crystals exhibit three groups of bands: the vibrations in the low- and medium-frequency ranges are mixed in character with approximately identical contributions of all sublattices, and the bands at higher frequencies are associated with the contributions of Ag, C ^VI and In, C ^VI (C ^VI = Se, Te) atoms. The position of these bands allows us to make the inference that, in the crystals under investigation, the In-C ^VI bonding is stronger than the Ag-C ^VI bonding.     

Interfaces between Al2O3 and beta-Ni(1-x)Al(x) alloys: complex structures and Ab initio thermodynamics

A methodology to study the structural stability of binary alloy/Al2O3 interfaces is developed by expanding the conventional ab initio thermodynamics to include the dependence on alloy composition. Results on beta-Ni(1-x)Al(x)/Al2O3 interfaces predict the existence of two types of stable interfaces. The stable interface at equilibrium with Al-rich or strictly 1:1 alloy contains an Al2-terminated Al2O3 surface and continues with NiAl layers, and the interface at equilibrium with Ni-rich alloy has Al accumulation but continues with a Ni-rich and then NiAl layers. Works of separation for the two interfaces are close to each other.     

Unified picture of the distribution of electric field gradients at Cu, O, and Tm sites in ReBa2Cu3O7−δ

An abundant set of published experimental NMR/NQR data on electric field gradients in ReBa₂Cu₃O_7−δ high temperature conductors, where Re=Y and Tm, is used as a test for the singlet-correlated band theory. Because of the unusual spectral weight (“capacity”) of this band, it has been possible to match the number of holes per lattice site to photoemission data on the energy spectrum and the location of the Fermi level. In the framework of a unified picture of the distribution of holes (charges) it has been possible for the first time to explain satisfactorily the observed electric field gradients at the Cu(1), Cu(2), O(1), O(2), O(3), and O(4) sites, as well as NMR and inelastic neutron scattering data on the crystal electric field at the Tm ions. Zh. éksp. Teor. Fiz. 111, 144–157 (January 1997)     

Ab initio calculations of phonon transport in ZnO and ZnS

We present an approach to calculate ballistic phonon transport that combines the atomistic Green’s function (AGF) method with ab initio results. For the interatomic potential we use the harmonic approach. The equilibrium positions of the atoms and the interatomic force constants (ifcs) are calculated using the ABINIT program package [X. Gonze et al., Z. Kristallogr. 220, 558 (2005)], which is based on density functional theory. Therefore, the presented approach is parameter free. From the Green’s function of the system we determine the density of states as well as the transmission function. The thermal conductance is obtained within the linear response regime. We apply this approach to bulk ZnO and bulk ZnS. Transmission functions for different transport directions for each material are presented. A comparison of the transmission function shows, that a ZnO/ZnS interface could be a promising phonon blocker. Adding such interfaces in ZnO or ZnS based thermoelectric devices could therefore increase the figure of merit.