Proton conducting oxide ceramics have shown potential for use in fuel cell technologies. Understanding the energy pathways for proton conduction could help us design more efficient fuel cell materials. This paper describes how octahedral tilting affects the relative energies of proton binding sites, transition states, and conduction pathways in cubic and pseudo-cubic perovskites. First, the structure for cubic and pseudo-cubic forms of BaTiO(3), BaZrO(3), CaTiO(3), and CaZrO(3), is found. Even when cubic symmetry is enforced, CaTiO(3), and CaZrO(3) exhibit octahedral tilting distortions characteristic of orthorhombic phases while BaTiO(3) and BaZrO(3) remain undistorted. Octahedral tilting gives rise to proton binding sites facilitating inter- and intra-octahedral proton transfer while the proton binding sites of undistorted perovskites facilitate only intra-octahedral proton transfer. The nudged elastic band method is used to find minimum energy paths between the proton binding sites. As distortions increase, inter-octahedral proton transfer barriers decrease while intra-octahedral proton transfer barriers increase. Concurrently, rotational barriers from oxygens facilitating inter-octahedral proton transfer increase while rotational barriers from oxygens facilitating intra-octahedral proton transfer decrease. Intra-octahedral transfer is the rate-limiting step to the lowest energy extended proton conduction pathway in all the perovskites considered.

We present a molecular dynamics based method for accurately computing short-range structural forces resulting from the overlap of spatially diffuse solid-liquid interfaces at wetted grain boundaries close to the melting point. The method is based on monitoring the fluctuations of the liquid layer width at different temperatures to extract the excess interfacial free energy as a function of this width. The method is illustrated for a high-energy Sigma9 twist boundary in pure Ni. The short-range repulsion driving premelting is found to be dominant in comparison to long-range dispersion and entropic forces and consistent with previous experimental findings that nanometer-scale layer widths may be observed only very close to the melting point.

In the present paper, the authors focus on proton conduction pathways in a cubic perovskite KTaO(3) and an orthorhombic perovskite SrZrO(3). Density functional theory with a generalized gradient approximation is used to find proton binding sites. The nudged elastic band method is used to find transition states between minima. With this potential energy map of binding and transition states, adjacency matrices and their analogs identify four types of conduction paths in KTaO(3). Distortions from these paths are seen in SrZrO(3). In both cases, the lowest energy path has an intraoctahedral transfer rate-limiting barrier. A Fourier analysis of the OH stretch in ab initio molecular dynamics simulations revealed a strongly redshifted OH stretch in SrZrO(3) relative to KTaO(3). Hence, an orthorhombic system with a lowest energy conduction path limited by an intraoctahedral barrier can exhibit a redshifted OH stretch.

ABSTRACT:Quantum-based models of how potential energies depend on charge are developed from a three-state model, at the level of neglecting state-to-state overlap. The energy as a function of charge is defined as proposed previously (Valone and Atlas, J Chem Phys 2004, 120, 7262). With this definition, addition of a third state smooths the derivatives of the energy model with respect to charge at integer values of charge that are in the interior of the allowed charge range. These derivatives are related to the chemical potential. At the dissociation limit, this model converges to established limits. Another dependence is proposed that uses two different charges simultaneously. The concepts are illustrated, with calculations on an OH molecule.