Anomalous enhancement of tetragonality in PbTiO3 induced by negative pressure

Using a first-principles approach based on density-functional theory, we find that a large tetragonal strain can be induced in PbTiO3 by application of a negative hydrostatic pressure. The structural parameters and the dielectric and dynamical properties are found to change abruptly near a crossover pressure, displaying a ``kinky'' behavior suggestive of proximity to a phase transition. Analogous calculations for BaTiO3 show that the same effect is also present there, but at much higher negative pressure. We investigate this unexpected behavior of PbTiO3 and discuss an interpretation involving a phenomenological description in terms of a reduced set of relevant degrees of freedom.Comment: 9 pages, with 9 postscript figures embedded. Uses REVTEX and epsf macros. Also available at http://www.physics.rutgers.edu/~dhv/preprints/st_pbti/index.htm

Self-consistent equation for an interacting Bose gas

We consider interacting Bose gas in thermal equilibrium assuming a positive and bounded pair potential $V(r)$ such that 0<\int d\br V(r) = a<\infty. Expressing the partition function by the Feynman-Kac functional integral yields a classical-like polymer representation of the quantum gas. With Mayer graph summation techniques, we demonstrate the existence of a self-consistent relation $\rho (\mu)=F(\mu-a\rho(\mu))$ between the density $\rho$ and the chemical potential $\mu$, valid in the range of convergence of Mayer series. The function $F$ is equal to the sum of all rooted multiply connected graphs. Using Kac's scaling V_{\gamma}(\br)=\gamma^{3}V(\gamma r) we prove that in the mean-field limit $\gamma\to 0$ only tree diagrams contribute and function $F$ reduces to the free gas density. We also investigate how to extend the validity of the self-consistent relation beyond the convergence radius of Mayer series (vicinity of Bose-Einstein condensation) and study dominant corrections to mean field. At lowest order, the form of function $F$ is shown to depend on single polymer partition function for which we derive lower and upper bounds and on the resummation of ring diagrams which can be analytically performed.Comment: 33 pages, 6 figures, submitted to Phys.Rev.

Lattice instabilities of PbZrO3/PbTiO3 [1:1] superlattices from first principles

Ab initio phonon calculations for the nonpolar reference structures of the (001), (110), and (111) PbZrO_3/PbTiO_3 [1:1] superlattices are presented. The unstable polar modes in the tetragonal (001) and (110) structures are confined in either the Ti- or the Zr-centered layers and display two-mode behavior, while in the cubic (111) case one-mode behavior is observed. Instabilities with pure oxygen character are observed in all three structures. The implications for the ferroelectric behavior and related properties are discussed.Comment: 12 pages, 2 figures, 7 tables, submitted to PR

Ab initio study of ferroelectric domain walls in PbTiO3

We have investigated the atomistic structure of the 180-degree and 90-degree domain boundaries in the ferroelectric perovskite compound PbTiO3 using a first-principles ultrasoft-pseudopotential approach. For each case we have computed the position, thickness and creation energy of the domain walls, and an estimate of the barrier height for their motion has been obtained. We find both kinds of domain walls to be very narrow with a similar width of the order of one to two lattice constants. The energy of the 90-dergree domain wall is calculated to be 35 mJ/m^2, about a factor of four lower than the energy of its 180-degree counterpart, and only a miniscule barrier for its motion is found. As a surprising feature we detected a small offset of 0.15-0.2 eV in the electrostatic potential across the 90-degree domain wall.Comment: 12 pages, with 9 postscript figures embedded. Uses REVTEX and epsf macros. Also available at http://www.physics.rutgers.edu/~dhv/preprints/bm_dw/index.htm

Theory of structural response to macroscopic electric fields in ferroelectric systems

We have developed and implemented a formalism for computing the structural response of a periodic insulating system to a homogeneous static electric field within density-functional perturbation theory (DFPT). We consider the thermodynamic potentials E(R,eta,e) and F(R,eta,e) whose minimization with respect to the internal structural parameters R and unit cell strain eta yields the equilibrium structure at fixed electric field e and polarization P, respectively. First-order expansion of E(R,eta,e) in e leads to a useful approximation in which R(P) and eta(P) can be obtained by simply minimizing the zero-field internal energy with respect to structural coordinates subject to the constraint of a fixed spontaneous polarization P. To facilitate this minimization, we formulate a modified DFPT scheme such that the computed derivatives of the polarization are consistent with the discretized form of the Berry-phase expression. We then describe the application of this approach to several problems associated with bulk and short-period superlattice structures of ferroelectric materials such as BaTiO3 and PbTiO3. These include the effects of compositionally broken inversion symmetry, the equilibrium structure for high values of polarization, field-induced structural phase transitions, and the lattice contributions to the linear and the non-linear dielectric constants.Comment: 19 pages, with 15 postscript figures embedded. Uses REVTEX4 and epsf macros. Also available at http://www.physics.rutgers.edu/~dhv/preprints/sai_pol/index.htm

Structural and dielectric properties of Sr2_{2}TiO4_{4} from first principles

We have investigated the structural and dielectric properties of Sr$_{2}$TiO$_{4}$,the first member of the Sr$_{n+1}$Ti$_{n}$O$_{3n+1}$ Ruddlesden-Popper series, within density functional theory. Motivated by recent work in which thin films of Sr$_{2}$TiO$_{4}$ were grown by molecular beam epitaxy (MBE) on SrTiO$_{3}$ substrates, the in-plane lattice parameter was fixed to the theoretically optimized lattice constant of cubic SrTiO$_{3}$ (n=$\infty$), while the out-of-plane lattice parameter and the internal structural parameters were relaxed. The fully relaxed structure was also investigated. Density functional perturbation theory was used to calculate the zone-center phonon frequencies, Born effective charges, and the electronic dielectric permittivity tensor. A detailed study of the contribution of individual infrared-active modes to the static dielectric permittivity tensor was performed. The calculated Raman and infrared phonon frequencies were found to be in agreement with experiment where available. Comparisons of the calculated static dielectric permittivity with experiments on both ceramic powders and epitaxial thin films are discussed.Comment: 11 pages, 1 figure, 8 tables, submitted to Phys. Rev.

Electronic and structural properties of vacancies on and below the GaP(110) surface

We have performed total-energy density-functional calculations using first-principles pseudopotentials to determine the atomic and electronic structure of neutral surface and subsurface vacancies at the GaP(110) surface. The cation as well as the anion surface vacancy show a pronounced inward relaxation of the three nearest neighbor atoms towards the vacancy while the surface point-group symmetry is maintained. For both types of vacancies we find a singly occupied level at mid gap. Subsurface vacancies below the second layer display essentially the same properties as bulk defects. Our results for vacancies in the second layer show features not observed for either surface or bulk vacancies: Large relaxations occur and both defects are unstable against the formation of antisite vacancy complexes. Simulating scanning tunneling microscope pictures of the different vacancies we find excellent agreement with experimental data for the surface vacancies and predict the signatures of subsurface vacancies.Comment: 10 pages, 6 figures, Submitted to Phys. Rev. B, Other related publications can be found at http://www.rz-berlin.mpg.de/th/paper.htm

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

Phonons and related properties of extended systems from density-functional perturbation theory

This article reviews the current status of lattice-dynamical calculations in crystals, using density-functional perturbation theory, with emphasis on the plane-wave pseudo-potential method. Several specialized topics are treated, including the implementation for metals, the calculation of the response to macroscopic electric fields and their relevance to long wave-length vibrations in polar materials, the response to strain deformations, and higher-order responses. The success of this methodology is demonstrated with a number of applications existing in the literature.Comment: 52 pages, 14 figures, submitted to Review of Modern Physic

First-principles study of the effect of charge on the stability of a diamond nanocluster surface

Effects of net charge on the stability of the diamond nanocluster are investigated using the first-principles pseudopotential method with the local density approximation. We find that the charged nanocluster favors the diamond phase over the reconstruction into a fullerene-like structure. Occupying the dangling bond orbitals in the outermost surface, the excess charge can stabilize the bare diamond surface and destabilize the C-H bond on the hydrogenated surface. In combination with recent experimental results, our calculations suggest that negative charging could promote the nucleation and further growth of low-pressure diamond.open8