Lattice effects on the formation of oxygen vacancies in perovskite thin films

We use first-principles methods to investigate the effects of collective lattice excitations on the formation of oxygen vacancies in perovskite thin films. We find that phonons play a crucial role on the strain-mediated control of defect chemistry at finite temperatures. In particular, zero-temperature oxygen vacancy formation trends deduced as a function of epitaxial strain can be fully reversed near room temperature. Our first-principles calculations evidence a direct link between the lattice contribution to the oxygen vacancy free energy and the volume expansion that the system undergoes when is chemically reduced: The larger the resulting volume expansion, the more favorable thermal excitations are to point defect formation. However, the interplay between the vibrational vacancy entropy, or equivalently, chemical expansion, and epitaxial strain is difficult to generalise as this can be strongly influenced by underlying structural and magnetic transitions. In addition, we find that vacancy ordering can be largely hindered by the thermal lattice excitations.Comment: 5 pages, 5 figure

Superionicity and Polymorphism in Calcium Fluoride at High Pressure

We present a combined experimental and computational first-principles study of the superionic and structural properties of CaF2 at high P-T conditions. We observe an anomalous superionic behavior in the low-P fluorite phase that consists in a decrease of the normal-> superionic critical temperature with compression. This unexpected effect can be explained in terms of a P-induced softening of a zone-boundary $X$ phonon which involves exclusively fluorine displacements. Also we find that superionic conductivity is absent in the high-P cotunnite phase. Instead, superionicity develops in a new low-symmetry high-T phase that we identify as monoclinic (space group P2_1/c). We discuss the possibility of observing these intriguing phenomena in related isomorphic materials.Comment: 5 pages, 5 figure

The Limit of Mechanical Stability in Quantum Crystals: A Diffusion Monte Carlo Study of Solid 4He

We present a first-principles study of the energy and elastic properties of solid helium at pressures below the range in which is energetically stable. We find that the limit of mechanical stability in hcp 4He is $P_{s}$ = -33.82 bar, which lies significantly below the spinodal pressure found in the liquid phase (i.e., -9.6 bar). Furthermore, we show that the pressure variation of the transverse and longitudinal sound velocities close to $P_{s}$ do not follow a power law of the form $\propto \left( P - P_{s} \right)^{\gamma}$, in contrast to what is observed on the fluid.Comment: 4 pages, 4 figure

Possible superfluidity of molecular hydrogen in a two-dimensional crystal phase of sodium

We theoretically investigate the ground-state properties of a molecular para-hydrogen (p-H2) film in which crystallization is energetically frustrated by embedding sodium (Na) atoms periodically distributed in a triangular lattice. In order to fully deal with the quantum nature of p-H2 molecules, we employ the diffusion Monte Carlo method and realistic semi-empirical pairwise potentials describing the interactions between H2-H2 and Na-H2 species. In particular, we calculate the energetic, structural and superfluid properties of two-dimensional Na-H2 systems within a narrow density interval around equilibrium at zero temperature. In contrast to previous computational studies considering other alkali metal species such as rubidium and potassium, we find that the p-H2 ground-state is a liquid with a significantly large superfluid fraction of ~30%. The appearance of p-H2 superfluid response is due to the fact that the interactions between Na atoms and H2 molecules are less attractive than between H2 molecules. This induces a considerable reduction of the hydrogen density which favours the stabilization of the liquid phase.Comment: 7 pages, 6 figures, submitte

Electrostatic engineering of strained ferroelectric perovskites from first-principles

Design of novel artificial materials based on ferroelectric perovskites relies on the basic principles of electrostatic coupling and in-plane lattice matching. These rules state that the out-of-plane component of the electric displacement field and the in-plane components of the strain are preserved across a layered superlattice, provided that certain growth conditions are respected. Intense research is currently directed at optimizing materials functionalities based on these guidelines, often with remarkable success. Such principles, however, are of limited practical use unless one disposes of reliable data on how a given material behaves under arbitrary electrical and mechanical boundary conditions. Here we demonstrate, by focusing on the prototypical ferroelectrics PbTiO3 and BiFeO3 as testcases, how such information can be calculated from first principles in a systematic and efficient way. In particular, we construct a series of two-dimensional maps that describe the behavior of either compound (e.g. concerning the ferroelectric polarization and antiferrodistortive instabilities) at any conceivable choice of the in-plane lattice parameter, a, and out-of-plane electric displacement, D. In addition to being of immediate practical applicability to superlattice design, our results bring new insight into the complex interplay of competing degrees of freedom in perovskite materials, and reveal some notable instances where the behavior of these materials depart from what naively is expected.Comment: 13 pages, 9 figure

Ground-state properties and superfluidity of two- and quasi two-dimensional solid 4He

In a recent study we have reported a new type of trial wave function symmetric under the exchange of particles and which is able to describe a supersolid phase. In this work, we use the diffusion Monte Carlo method and this model wave function to study the properties of solid 4He in two- and quasi two-dimensional geometries. In the purely two-dimensional case, we obtain results for the total ground-state energy and freezing and melting densities which are in good agreement with previous exact Monte Carlo calculations performed with a slightly different interatomic potential model. We calculate the value of the zero-temperature superfluid fraction \rho_{s} / \rho of 2D solid 4He and find that it is negligible in all the considered cases, similarly to what is obtained in the perfect (free of defects) three-dimensional crystal using the same computational approach. Interestingly, by allowing the atoms to move locally in the perpendicular direction to the plane where they are confined to zero-point oscillations (quasi two-dimensional crystal) we observe the emergence of a finite superfluid density that coexists with the periodicity of the system.Comment: 16 pages, 8 figure