A More Accurate Generalized Gradient Approximation for Solids

We present a new nonempirical density functional generalized gradient approximation (GGA) that gives significant improvements for lattice constants, crystal structures, and metal surface energies over the most popular Perdew-Burke-Ernzerhof (PBE) GGA. The new functional is based on a diffuse radial cutoff for the exchange-hole in real space, and the analytic gradient expansion of the exchange energy for small gradients. There are no adjustable parameters, the constraining conditions of PBE are maintained, and the functional is easily implemented in existing codes.Comment: 5 pages, corrected the errors of the sublimation energy of Ih ic

Origin of the large phonon band-gap in SrTiO3 and the vibrational signatures of ferroelectricity in ATiO3 perovskite: First principles lattice dynamics and inelastic neutron scattering of PbTiO3, BaTiO3 and SrTiO3

We report first principles density functional perturbation theory calculations and inelastic neutron scattering measurements of the phonon density of states, dispersion relations and electromechanical response of PbTiO3, BaTiO3 and SrTiO3. The phonon density-of-states of the quantum paraelectric SrTiO3 is found to be fundamentally distinct from that of ferroelectric PbTiO3 and BaTiO3 with a large 70-90 meV phonon band-gap. The phonon dispersion and electromechanical response of PbTiO3 reveal giant anisotropies. The interplay of covalent bonding and ferroelectricity, strongly modulates the electromechanical response and give rise to spectacular signatures in the phonon spectra. The computed charge densities have been used to study the bonding in these perovskites. Distinct bonding characteristics in the ferroelectric and paraelectric phases give rise to spectacular vibrational signatures. While a large phonon band-gap in ATiO3 perovskites seems a characteristic of quantum paraelectrics, anisotropy of the phonon spectra correlates well with ferroelectric strength. These correlations between the phonon spectra and ferroelectricity, can guide future efforts at custom designing still more effective piezoelectrics for applications. These results suggest that vibrational spectroscopy can help design novel materials.Comment: 11 pages, 4 color figures and 2 Table

Phonon Properties of Knbo3 and Ktao3 from First-Principles Calculations

The frequencies of transverse-optical $\Gamma$ phonons in KNbO$_3$ and KTaO$_3$ are calculated in the frozen-phonon scheme making use of the full-potential linearized muffin-tin orbital method. The calculated frequencies in the cubic phase of KNbO$_3$ and in the tetragonal ferroelectric phase are in good agreement with experimental data. For KTaO$_3$, the effect of lattice volume was found to be substantial on the frequency of the soft mode, but rather small on the relative displacement patterns of atoms in all three modes of the $T_{1u}$ symmetry. The TO frequencies in KTaO$_3$ are found to be of the order of, but somehow higher than, the corresponding frequencies in cubic KNbO$_3$.Comment: 8 pages + 1 LaTeX figure, Revtex 3.0, SISSA-CM-94-00

Non-cubic layered structure of Ba(1-x)K(x)BiO3 superconductor

Bismuthate superconductor Ba(1-x)K(x)BiO3 (x=0.27-0.49, Tc=25-32K) grown by an electrolysis technique was studied by electron diffraction and high-resolution electron microscopy. The crystalline structure thereof has been found to be non-cubic, of the layered nature, and non-centrosymmetric, with the lattice parameters a ~ ap, c ~ 2ap (ap is a simple cubic perovskite cell parameter) containing an ordered arrangement of barium and potassium. The evidence for the layered nature of the bismuthate superconductor removes the principal crystallographic contradiction between bismuthate and cuprate high-Tc superconductors.Comment: 4 pages, 3 figures, to be published in Physical Review B as a Rapid Communicatio

Born Effective Charges of Barium Titanate: band by band decomposition and sensitivity to structural features

The Born effective charge tensors of Barium Titanate have been calculated for each of its 4 phases. Large effective charges of Ti and O, also predicted by shell model calculations and made plausible by a simplified model, reflect the partial covalent character of the chemical bond. A band by band decomposition confirms that orbital hybridization is not restricted to Ti and O atoms but also involves Ba which appears more covalent than generally assumed. Our calculations reveal a strong dependence of the effective charges on the atomic positions contrasting with a relative insensitivity on isotropic volume changes.Comment: 13 page

Dynamic force microscopy for imaging of viruses under physiological conditions

Dynamic force microscopy (DFM) allows imaging of the structure and the assessment of the function of biological specimens in their physiological environment. In DFM, the cantilever is oscillated at a given frequency and touches the sample only at the end of its downward movement. Accordingly, the problem of lateral forces displacing or even destroying bio-molecules is virtually inexistent as the contact time and friction forces are reduced. Here, we describe the use of DFM in studies of human rhinovirus serotype 2 (HRV2) weakly adhering to mica surfaces. The capsid of HRV2 was reproducibly imaged without any displacement of the virus. Release of the genomic RNA from the virions was initiated by exposure to low pH buffer and snapshots of the extrusion process were obtained. In the following, the technical details of previous DFM investigations of HRV2 are summarized

The physics of dynamical atomic charges: the case of ABO3 compounds

Based on recent first-principles computations in perovskite compounds, especially BaTiO3, we examine the significance of the Born effective charge concept and contrast it with other atomic charge definitions, either static (Mulliken, Bader...) or dynamical (Callen, Szigeti...). It is shown that static and dynamical charges are not driven by the same underlying parameters. A unified treatment of dynamical charges in periodic solids and large clusters is proposed. The origin of the difference between static and dynamical charges is discussed in terms of local polarizability and delocalized transfers of charge: local models succeed in reproducing anomalous effective charges thanks to large atomic polarizabilities but, in ABO3 compounds, ab initio calculations favor the physical picture based upon transfer of charges. Various results concerning barium and strontium titanates are presented. The origin of anomalous Born effective charges is discussed thanks to a band-by-band decomposition which allows to identify the displacement of the Wannier center of separated bands induced by an atomic displacement. The sensitivity of the Born effective charges to microscopic and macroscopic strains is examined. Finally, we estimate the spontaneous polarization in the four phases of barium titanate.Comment: 25 pages, 6 Figures, 10 Tables, LaTe

Semiempirical Hartree-Fock calculations for KNbO3

In applying the semiempirical intermediate neglect of differential overlap (INDO) method based on the Hartree-Fock formalism to a cubic perovskite-based ferroelectric material KNbO3, it was demonstrated that the accuracy of the method is sufficient for adequately describing the small energy differences related to the ferroelectric instability. The choice of INDO parameters has been done for a system containing Nb. Based on the parametrization proposed, the electronic structure, equilibrium ground state structure of the orthorhombic and rhombohedral phases, and Gamma-TO phonon frequencies in cubic and rhombohedral phases of KNbO3 were calculated and found to be in good agreement with the experimental data and with the first-principles calculations available.Comment: 7 pages, 2 Postscript figures, uses psfig.tex. To be published in Phys.Rev.B 54, No.4 (1996