Relative phase stability and lattice dynamics of NaNbO3_3 from first-principles calculations

We report total energy calculations for different crystal structures of NaNbO$_3$ over a range of unit cell volumes using the all-electron full-potential (L)APW method. We employed both the local-density approximation (LDA) and the Wu-Cohen form of the generalized gradient approximation (GGA-WC) to test the accuracy of these functionals for the description of the complex structural behavior of NaNbO$_3$. We found that LDA not only underestimates the equilibrium volume of the system but also predicts an incorrect ground state for this oxide. The GGA-WC functional, on the other hand, significantly improves the equilibrium volume and provides relative phase stability in better agreement with experiments. We then use the GGA-WC functional for the calculation of the phonon dispersion curves of cubic NaNbO$_3$ to identify the presence of structural instabilities in the whole Brillouin zone. Finally, we report comparative calculations of structural instabilities as a function of volume in NaNbO$_3$ and KNbO$_3$ to provide insights for the understanding of the structural behavior of K$_{1-x}$Na$_x$NbO$_3$ solid solutions.Comment: Accepted for publication in Physical Review

Temperature-driven phase transitions in SrBi2_2Ta2_2O9_9 from first-principles calculations

The phase transition sequence of SrBi$_2$Ta$_2$O$_9$ is investigated using a shell model with parameters fitted to first-principles calculations. We show that the complex interplay between polar and nonpolar instabilities leads to the presence of two phase transitions, corroborating the existence of an intermediate orthorhombic paraelectric phase. This phase is characterized by the rotation of the TaO$_6$ octahedra around the a-axis. We show that this phase can be also detected from the dielectric response of the material. The present approach constitutes a powerful tool for a theoretical prediction of intermediate phases, not yet observed experimentally, in other Aurivillius compounds

Effects of the antiferrodistortive instability on the structural behavior of BaZrO3_3 by atomistic simulations

Recently, the possibility of a low-temperature non-cubic phase in BaZrO$_3$ has generated engaging discussions about its true ground state and the consequences on its physical properties. In this paper, we investigate the microscopic behavior of the BaZrO$_3$ cubic phase by developing a shell model from $ab~initio$ calculations and by performing molecular dynamics simulations at finite temperature and under negative pressure. We study three different scenarios created by tuning the intensities of the antiferrodistortive (AFD) instabilities, and consequently, the sequence of phase transitions with temperature. From a detailed analysis of the cubic phase at atomic scale, we find that oxygen octahedra are barely distorted, present rotation angles that may oscillate with significant amplitudes, are AFD correlated with their closest neighbors on the plane perpendicular to the pseudocubic rotation axis exhibiting $(0 0 a^-)$-type ordering, and form instantaneous, dynamic and unstable domains over time. Our simulations support the existence of nanoregions with short-range ordering in cubic BaZrO$_3$ associated with experimentally observed anomalies and unveil that they can exist regardless of whether or not structural phase transitions related with AFD distortions occur at lower temperatures.Comment: 10 pages, 8 figure

First principles based atomistic modeling of phase stability in PMN-xPT

We have performed molecular dynamics simulations using a shell model potential developed by fitting first principles results to describe the behavior of the relaxor-ferroelectric (1-x)PbMg1/3Nb2/3O3-xPbTiO3 (PMN-xPT) as function of concentration and temperature, using site occupancies within the random site model. In our simulations, PMN is cubic at all temperatures and behaves as a polar glass. As a small amount of Ti is added, a weak polar state develops, but structural disorder dominates, and the symmetry is rhombohedral. As more Ti is added the ground state is clearly polar and the system is ferroelectric, but with easy rotation of the polarization direction. In the high Ti content region, the solid solution adopts ferroelectric behavior similar to PT, with tetragonal symmetry. The ground state sequence with increasing Ti content is R-MB-O-MC-T. The high temperature phase is cubic at all compositions. Our simulations give the slope of the morphotropic phase boundaries, crucial for high temperature applications. We find that the phase diagram PMN-xPT can be understood within the random site model.Comment: 27 pages, 9 figure