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

The Role of Density Functional Theory Methods in the Prediction of Nanostructured Gas-Adsorbent Materials

With the advent of new synthesis and large-scale production technologies, nanostructured gas-adsorbent materials (GAM) like carbon nanocomposites and metal-organic frameworks are becoming increasingly more influential in our everyday lives. First-principles methods based on density functional theory (DFT) have been pivotal in establishing the rational design of GAM, a factor which has tremendously boosted their development. However, DFT methods are not perfect and due to the stringent accuracy thresholds demanded in modelling of GAM (i.e., exact binding energies to within ~0.01 eV) these techniques may provide erroneous conclusions in some challenging situations. Examples of problematic circumstances include gas-adsorption processes in which both electronic long-range exchange and nonlocal correlations are important, and systems where many-body energy and Coulomb screening effects cannot be disregarded. In this critical review, we analyse recent efforts done in the assessment of the performance of DFT methods in the prediction and understanding of GAM. Our inquiry is constrained to the areas of hydrogen storage and carbon capture and sequestration, for which we expose a number of unresolved modelling controversies and define a set of best practice simulation principles. Also, we identify the subtle problems found in the generalization of DFT benchmark studies performed in model cluster systems to real materials, and discuss effective approaches to circumvent them. The increasing awareness of the strengths and imperfections of DFT methods in the simulation of gas-adsorption phenomena should lead in the medium term to more precise, and hence even more fruitful, ab initio engineering of GAM.Comment: 27 pages, 10 figures, review articl

In the search of new electrocaloric materials: Fast ion conductors

We analyse the effects of applying an electric field on the critical temperature, Ts, at which superionicity appears in archetypal fast ion conductor CaF2 by means of molecular dynamics simulations. We find that the onset of superionicity can be reduced by about 100K when relatively small electric fields of ~50KV/cm are employed. Under large enough electric fields, however, ionic conductivity is depleted. The normal to superionic phase transition is characterised by a large increase of entropy, thereby sizeable electrocaloric effects can be realised in fast ion conductors that are promising for solid-state cooling applications.Comment: 2 pages, 2 figure

First-principles modeling of three-body interactions in highly compressed solid helium

We present a new set of three-body interaction models based on the Bruch-McGee (BM) potential that are suitable for the study of the energy, structural and elastic properties of solid 4He at high pressure. Our ab initio three-body potentials are obtained from the fit to total energies and atomic forces computed with the van der Waals density functional theory method due to Grimme, and represent an improvement with respect to previously reported three-body interaction models. In particular, we show that some of the introduced BM parametrizations reproduce closely the experimental equation of state and bulk modulus of solid helium up to a pressure of ~ 60 GPa, when used in combination with standard pairwise interaction models in diffusion Monte Carlo simulations. Importantly, we find that recent predictions reporting a surprisingly small variation of the kinetic energy and Lindeman ratio on quantum crystals under increasing pressure are likely to be artifacts produced by the use of incomplete interaction models. Also, we show that the experimental variation of the shear modulus, C44, at P < 25 GPa can be quantitatively described with the new set of three-body BM potentials. At higher pressures, however, the agreement between our C44 results and experiments deteriorates and thus we argue that higher order many-body terms in the expansion of the atomic interactions probably are necessary in order to better describe elasticity in very dense solid 4He.Comment: 11 pages, 7 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

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