First-principles theory of ferroelectric phase transitions for perovskites: The case of BaTiO3

We carry out a completely first-principles study of the ferroelectric phase transitions in BaTiO$_3$. Our approach takes advantage of two features of these transitions: the structural changes are small, and only low-energy distortions are important. Based on these observations, we make systematically improvable approximations which enable the parameterization of the complicated energy surface. The parameters are determined from first-principles total-energy calculations using ultra-soft pseudopotentials and a preconditioned conjugate-gradient scheme. The resulting effective Hamiltonian is then solved by Monte Carlo simulation. The calculated phase sequence, transition temperatures, latent heats, and spontaneous polarizations are all in good agreement with experiment. We find the transitions to be intermediate between order-disorder and displacive character. We find all three phase transitions to be of first order. The roles of different interactions are discussed.Comment: 33 pages latex file, 9 figure

Structure and apparent topography of TiO2 (110) surfaces

We present self-consistent ab-initio total-energy and electronic-structure calculations on stoichiometric and non-stoichiometric TiO2 (110) surfaces. Scanning tunneling microscopy (STM) topographs are simulated by calculating the local electronic density of states over an energy window appropriate for the experimental positive-bias conditions. We find that under these conditions the STM tends to image the undercoordinated Ti atoms, in spite of the physical protrusion of the O atoms, giving an apparent reversal of topographic contrast on the stoichiometric 1x1 or missing-row 2x1 surface. We also show that both the interpretation of STM images and the direct comparison of surface energies favor an added-row structure over the missing-row structure for the oxygen-deficient 2x1 surface.Comment: 6 pages, two-column style with 5 postscript figures embedded. Uses REVTEX and epsf macros. Also available at http://www.physics.rutgers.edu/~dhv/preprints/index.html#ng_tio

Electronic structure of periodic curved surfaces -- continuous surface versus graphitic sponge

We investigate the band structure of electrons bound on periodic curved surfaces. We have formulated Schr\"{o}dinger's equation with the Weierstrass representation when the surface is minimal, which is numerically solved. Bands and the Bloch wavefunctions are basically determined by the way in which the ``pipes'' are connected into a network, where the Bonnet(conformal)-transformed surfaces have related electronic strucutres. We then examine, as a realisation of periodic surfaces, the tight-binding model for atomic networks (``sponges''), where the low-energy spectrum coincides with those for continuous curved surfaces.Comment: 4 page

Accurate calculation of polarization-related quantities in semiconductors

We demonstrate that polarization-related quantities in semiconductors can be predicted accurately from first-principles calculations using the appropriate approach to the problem, the Berry-phase polarization theory. For III-V nitrides, our test case, we find polarizations, polarization differences between nitride pairs, and piezoelectric constants quite close to their previously established values. Refined data are nevertheless provided for all the relevant quantities.Comment: RevTeX 4 pages, no figure

First-principles study of (BiScO3){1-x}-(PbTiO3){x} piezoelectric alloys

We report a first-principles study of a class of (BiScO3)_{1-x}-(PbTiO3)_x (BS-PT) alloys recently proposed by Eitel et al. as promising materials for piezoelectric actuator applications. We show that (i) BS-PT displays very large structural distortions and polarizations at the morphotropic phase boundary (MPB) (we obtain a c/a of ~1.05-1.08 and P_tet of ~1.1 C/m^2); (ii) the ferroelectric and piezoelectric properties of BS-PT are dominated by the onset of hybridization between Bi/Pb-6p and O-2p orbitals, a mechanism that is enhanced upon substitution of Pb by Bi; and (iii) the piezoelectric responses of BS-PT and Pb(Zr_{1-x}Ti_x)O3 (PZT) at the MPB are comparable, at least as far as the computed values of the piezoelectric coefficient d_15 are concerned. While our results are generally consistent with experiment, they also suggest that certain intrinsic properties of BS-PT may be even better than has been indicated by experiments to date. We also discuss results for PZT that demonstrate the prominent role played by Pb displacements in its piezoelectric properties.Comment: 6 pages, with 3 postscript figures embedded. Uses REVTEX and epsf macros. Also available at http://www.physics.rutgers.edu/~dhv/preprints/ji_bi/index.htm

Modeling the momentum distributions of annihilating electron-positron pairs in solids

Measuring the Doppler broadening of the positron annihilation radiation or the angular correlation between the two annihilation gamma quanta reflects the momentum distribution of electrons seen by positrons in the material.Vacancy-type defects in solids localize positrons and the measured spectra are sensitive to the detailed chemical and geometric environments of the defects. However, the measured information is indirect and when using it in defect identification comparisons with theoretically predicted spectra is indispensable. In this article we present a computational scheme for calculating momentum distributions of electron-positron pairs annihilating in solids. Valence electron states and their interaction with ion cores are described using the all-electron projector augmented-wave method, and atomic orbitals are used to describe the core states. We apply our numerical scheme to selected systems and compare three different enhancement (electron-positron correlation) schemes previously used in the calculation of momentum distributions of annihilating electron-positron pairs within the density-functional theory. We show that the use of a state-dependent enhancement scheme leads to better results than a position-dependent enhancement factor in the case of ratios of Doppler spectra between different systems. Further, we demonstrate the applicability of our scheme for studying vacancy-type defects in metals and semiconductors. Especially we study the effect of forces due to a positron localized at a vacancy-type defect on the ionic relaxations.Comment: Submitted to Physical Review B on September 1 2005. Revised manuscript submitted on November 14 200

A real-space grid implementation of the Projector Augmented Wave method

A grid-based real-space implementation of the Projector Augmented Wave (PAW) method of P. E. Blochl [Phys. Rev. B 50, 17953 (1994)] for Density Functional Theory (DFT) calculations is presented. The use of uniform 3D real-space grids for representing wave functions, densities and potentials allows for flexible boundary conditions, efficient multigrid algorithms for solving Poisson and Kohn-Sham equations, and efficient parallelization using simple real-space domain-decomposition. We use the PAW method to perform all-electron calculations in the frozen core approximation, with smooth valence wave functions that can be represented on relatively coarse grids. We demonstrate the accuracy of the method by calculating the atomization energies of twenty small molecules, and the bulk modulus and lattice constants of bulk aluminum. We show that the approach in terms of computational efficiency is comparable to standard plane-wave methods, but the memory requirements are higher.Comment: 13 pages, 3 figures, accepted for publication in Physical Review

Spontaneous polarization and piezoelectric constants of III-V nitrides

The spontaneous polarization, dynamical Born charges, and piezoelectric constants of the III-V nitrides AlN, GaN, and InN are studied ab initio using the Berry phase approach to polarization in solids. The piezoelectric constants are found to be up 10 times larger than in conventional III-V's and II-VI's, and comparable to those of ZnO. Further properties at variance with those of conventional III-V compounds are the sign of the piezoelectric constants (positive as in II-VI's) and the very large spontaneous polarization.Comment: RevTeX 4 pages, improved upon revie

Dynamics of Phononic Dissipation at the Atomic Scale: Dependence on Internal Degrees of Freedom

Dynamics of dissipation of a local phonon distribution to the substrate is a key issue in friction between sliding surfaces as well as in boundary lubrication. We consider a model system consisting of an excited nano-particle which is weakly coupled with a substrate. Using three different methods we solve the dynamics of energy dissipation for different types of coupling between the nano-particle and the substrate, where different types of dimensionality and phonon densities of states were also considered for the substrate. In this paper, we present our analysis of transient properties of energy dissipation via phonon discharge in the microscopic level towards the substrate. Our theoretical analysis can be extended to treat realistic lubricant molecules or asperities, and also substrates with more complex densities of states. We found that the decay rate of the nano-particle phonons increases as the square of the interaction constant in the harmonic approximation.Comment: 10 pages, 6 figures, submitted to Phys. Rev.

Fermi level alignment in molecular nanojunctions and its relation to charge transfer

The alignment of the Fermi level of a metal electrode within the gap of the hi ghest occupied (HOMO) and lowest unoccupied orbital (LUMO) of a molecule is a key quantity in molecular electronics, which can vary the electron transparency of a single molecule junction by orders of magnitude. We present a quantitative analysis of the relation between this level alignment (which can be estimated from charging free molecules) and charge transfer for bipyridine and biphenyl dithiolate (BPDT) molecules attached to gold leads based on density functional theory calculations. For both systems the charge distribution is defined by a balance between Pauli repulsion with subsequent electrostatic screening and the filling of the LUMO, where bipyridine loses electrons to the leads and BPDT gains electrons. As a direct consequence the Fermi level of the metal is found close to the LUMO for bipyridine and close to the HOMO for BPDT