Compositional Inversion Symmetry Breaking in Ferroelectric Perovskites

Ternary cubic perovskite compounds of the form A_(1/3)A'_(1/3)A''_(1/3)BO_3 and AB_(1/3)B'_(1/3)B''_(1/3)O_3, in which the differentiated cations form an alternating series of monolayers, are studied using first-principles methods. Such compounds are representative of a possible new class of materials in which ferroelectricity is perturbed by compositional breaking of inversion symmetry. For isovalent substitution on either sublattice, the ferroelectric double-well potential is found to persist, but becomes sufficiently asymmetric that minority domains may no longer survive. The strength of the symmetry breaking is enormously stronger for heterovalent substitution, so that the double-well behavior is completely destroyed. Possible means of tuning between these behaviors may allow for the optimization of resulting materials properties.Comment: 4 pages, two-column style with 3 postscript figures embedded. Uses REVTEX and epsf macros. Also available at http://www.physics.rutgers.edu/~dhv/preprints/index.html#sai_is

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

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

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