Ab initio and shell model studies of structural, thermoelastic and vibrational properties of SnO2 under pressure.

The pressure dependences of the structural, thermoelastic and vibrational properties of SnO2 in its rutile phase are studied, as well as the pressure-induced transition to a CaCl2-type phase. These studies have been performed by means of ab initio (AI) density functional theory calculations using the localized basis code SIESTA. The results are employed to develop a shell model (SM) for application in future studies of nanostructured SnO2. A good agreement of the SM results for the pressure dependences of the above properties with the ones obtained from present and previous AI calculations as well as from experiments is achieved. The transition is characterized by a rotation of the Sn-centered oxygen octahedra around the tetragonal axis through the Sn. This rotation breaks the tetragonal symmetry of the lattice and an orthorhombic distortion appears above the critical pressure P(c). A zone-center phonon of B1g symmetry in the rutile phase involves such rotation and softens on approaching Pc. It becomes an Ag mode which stabilizes with increasing pressure in the CaCl2 phase. This behavior, together with the softening of the shear modulus (C11-C12)/2 related to the orthorhombic distortion, allows a precise determination of a value for Pc. An additional determination is provided by the splitting of the basal plane lattice parameters. Both the AI and the experimentally observed softening of the B(1g) mode are incomplete, indicating a small discontinuity at the transition. However, all results show continuous changes in volume and lattice parameters, indicating a second-order transition. All these results indicate that there should be sufficient confidence for the future employment of the shell model.

Ab initio studies of the para- and antiferroelectric structures and local polarized configurations in NH4H2PO4.

A study of differently polarized structures relevant to the H-bonded antiferroelectric (AFE) compound NH(4)H(2)PO(4) (ADP) is performed by first-principles calculations in the framework of the density functional theory. The calculated structures for the AFE and paraelectric (PE) phases are found in general good agreement with the available experimental data. We study the energetics and relative stability of different polarized clusters embedded in a PE matrix of ADP. We find that local ferroelectric and AFE clusters are stable and may coexist in the PE phase, which explains the coexistence of both type of microregions determined by electron spin probe measurements above the AFE-PE transition temperature. The dependency with the O-H···O bridge length of the energy barrier heights for proton transfer is studied for coordinated proton displacements along the bridges within clusters of different sizes. This dependency may have implications for the geometric isotopic effects on T(c). We analyze Mulliken orbital and bond populations which confirm the existence of a charge flow within the NH(4)(+) ion, an essential fact for the stabilization of the AFE phase over other possible polarized structures. This charge transfer is correlated with the optimization of the N-H···O bridges and with distortions of the NH(4)(+) group.

Origin of antiferroelectricity in NH4H2PO4 from first principles.

The low-temperature antiferroelectric (AFE) phase of NH4H2PO4 corresponds to H ordering in O-H-O bridges leading to H2PO4 group polarizations perpendicular to the tetragonal c axis and alternating in chains. We determine the microscopic origin of such order by means of first-principles calculations in the framework of the density functional theory. The formation of N-Hcdots, three dots, centeredO bridges with correlated charge transfers and NH4+ group distortions turn out to be essential in stabilizing the AFE configuration against a c-polarized ferroelectric (FE) phase, as well as other FE states polarized perpendicular to the c axis. These FE states lie only a few meV above the AFE phase, which explains the observation of FE-AFE phase coexistence near the AFE transition.

Interface effects in ferroelectric PbTiO3 ultrathin films on a paraelectric substrate.

Interface effects on the ferroelectric behavior of PbTiO3 ultrathin films deposited on a SrTiO3 substrate are investigated using an interatomic potential approach with parameters fitted to first-principles calculations. We find that the correlation of atomic displacements across the film-substrate interface is crucial for the stabilization of the ferroelectric state in films a few unit cells thick. We show that the minimum film thickness for the appearance of a spontaneous polarized domain state is not an intrinsic property of the ferroelectric film but depends on the polarizability of the paraelectric substrate. We also observe that the substrate displays an induced polarization with an unusual oscillatory behavior.

Ferroelectricity and isotope effects in hydrogen-bonded KDP crystals.

Based on an accurate first principles description of the energetics in H-bonded potassium-dihydrogen-phosphate crystals, we conduct a first study of nuclear quantum effects and of the changes brought about by deuteration. Tunneling is allowed only for clusters involving correlated protons and heavy ion displacements, the main effect of deuteration being a depletion of the proton probability density at the O-H-O bridge center, which in turn weakens its proton-mediated covalent bonding. The ensuing lattice expansion couples self-consistently with the proton off-centering, thus explaining both the giant isotope effect and its close connection with geometrical effects.