Ethane under pressure revisited using x-ray diffraction, Raman spectroscopy, infrared absorption, and ab initio calculations up to 150 GPa.

Ethane (C2H6) is anticipated to be the most stable compound within the carbon-hydrogen system under the 100 GPa pressure range. Nevertheless, the properties of ethane under pressure are still poorly documented. Here, we present a comprehensive study of the structural and vibrational properties of C2H6 in a diamond anvil cell at pressures up to 150 GPa. To obtain detailed data, ethane single-crystal was grown in a helium pressure-transmitting medium. Utilizing single-crystal x-ray diffraction, the distortion mechanism between the tetragonal and monoclinic phases, occurring over the 3.2-5.2 GPa pressure range, is disclosed. Subsequently, no phase transition is observed up to 150 GPa. The accurately measured compression curve is compared to various computational approximations. The vibrational modes measured by Raman spectroscopy and infrared absorption are well identified, and their evolution is well reproduced by ab initio calculations. In particular, an unusual anticrossing phenomenon occurs near 40 GPa between a rocking and a stretching mode, likely attributable to intermolecular interactions through hydrogen bonding.

High pressure polymorphism of LiBH4 and of NaBH4.

The pressure-induced structural changes in LiBH4 and in NaBH4 have been investigated experimentally up to 290 GPa by coupling Raman spectroscopy, infrared absorption spectroscopy and synchrotron X-ray diffraction. This data set is also analysed in the light of Density Functional Theory calculations performed up to 600 GPa. The [BH4]- unit appears to be remarkably resistant under pressure. NaBH4 remains stable in the known Pnma γ-phase up to 200 GPa and calculations predict a transition to a metallic polymeric C2/c phase at about 480 GPa. LiBH4 is confirmed to exhibit a richer polymorphism. A new Pnma orthorhombic phase VI is found to be stable above 60 GPa and there are hints of a possible phase VII above 160 GPa. DFT calculations predict that two other high pressure LiBH4 phases should appear at about 290 and 428 GPa. A very slight solubility of H2 inside phases II, III and V of LiBH4 is observed. A NaBH4(H2)0.5 complex is predicted to be stable above 150 GPa.

Structural, electronic and energetic properties of uranium-americium mixed oxides [Formula: see text] using DFT[Formula: see text] calculations.

In this paper, we determine for the first time the electronic, structural and energetic properties of [Formula: see text] mixed oxides in the entire range of Am content using the generalized gradient approximation (GGA)[Formula: see text] in combination with the special quasirandom structure (SQS) approach to reproduce chemical disorder. This study reveals that in [Formula: see text] oxides, Am cations act as electron acceptors, whereas U cations act as electron donors showing a fundamental difference with [Formula: see text] or [Formula: see text] in which there is no cation valence change in stoichiometric conditions compared to the pure oxides. We show for the first time that the lattice parameter of stoichiometric [Formula: see text] follows a linear evolution which is the structural signature of an ideal solid solution behavior. Finally, using two approaches (SQS and parametric), we show by assessing the enthalpy of mixing that there is no phase separation in the whole range of Am concentration.

Isotope effect on hydrogen bond symmetrization in hydrogen and deuterium fluoride crystals by molecular dynamics simulation.

The isotope effect on the collective proton/deuteron transfer in hydrogen and deuterium fluoride crystals has been investigated at 100 K by ab initio quantum-thermal-bath path-integral molecular dynamics (QTB-PIMD) simulation. The deuterons within a planar zigzag chain of the orthorhombic structure simultaneously flip between covalent and hydrogen bonds due to the barrier crossing through tunnelling. The height of the corresponding static barrier normalized for one deuteron is 29.2 meV. In the HF crystal, all the protons are located at the center of the heavy-atom distance. This evidences the symmetrization of the H-bonds, and indicates that the proton zero-point energy is above the barrier top. The decrease of the heavy-atom distance due to quantum fluctuations in both HF and DF crystals corresponds to a large decrease and an increase of the hydrogen and covalent bond lengths, respectively. Upon deuteration, the increase of the heavy-atom distance (Ubbelohde effect) is in agreement with experimental data.

Site Selectivity of Hydride in Early-Transition-Metal Ruddlesden-Popper Oxyhydrides.

Layered perovskite titanium oxyhydrides have been prepared by low-temperature topochemical CaH2 reduction from Ruddlesden-Popper Sr n+1Ti nO3 n+1 phases ( n = 1, 2) and structurally characterized by combined synchrotron X-ray and neutron diffraction data refinements. In the single-layered Sr2TiO3.91(2)D0.14(1) material, hydride anions are statistically disordered with oxides on the apical site only, as opposed to known transition-metal oxyhydrides exhibiting a preferred occupation of the equatorial site. This unprecedented site selectivity of H- has been reproduced by periodic DFT+ U calculations, emphasizing for the hydride defect a difference in formation energy of 0.24 eV between equatorial and apical sites. In terms of electronic structure, the model system Sr2TiO3.875H0.125 is found to be slightly metallic and the released electron remains mostly delocalized over several Ti atoms. On the other hand, hydride anions in the double-layered Sr3Ti2O6.20H0.12 material show a clear preference for the bridging apical site within the perovskite slabs, as confirmed by DFT calculations on the Sr3Ti2O6.875H0.125 model system. Finally, the influence of the B-site chemical nature on the hydride site selectivity for early 3d transition metals is theoretically explored in the single-layered system by substituting vanadium for titanium. The V3+ electronic polaron is suggested to play a role in stabilizing H- on the equatorial site in Sr2VO4- xH x for x = 0.125.

Vacancies and holes in bulk and at 180° domain walls in lead titanate.

Domain walls (DWs) in ferroic materials exhibit a plethora of unexpected properties that are different from the adjacent ferroic domains. Still, the intrinsic/extrinsic origin of these properties remains an open question. Here, density functional theory calculations are used to investigate the interaction between vacancies and 180° DWs in the prototypical ferroelectric PbTiO3, with a special emphasis on cationic vacancies and released holes. All vacancies are more easily formed within the DW than in the domains. This is interpreted, using a phenomenological model, as the partial compensation of an extra-tensile stress when the defect is created inside the DW. Oxygen vacancies are found to be always fully ionized, independently of the thermodynamic conditions, while cationic vacancies can be either neutral or partially ionized (oxygen-rich conditions), or fully ionized (oxygen-poor conditions). Therefore, in oxidizing conditions, holes are induced by neutral and partially ionized Pb vacancies. In the bulk PbTiO3, these holes are more stable as delocalized rather than small polarons, but at DWs, the two forms are found to be possible.

Reply to the 'Comment on "Proton transport in barium stannate: classical, semi-classical and quantum regime"'.

We respond to the erroneous criticisms about our modeling of proton transport in barium stannate [G. Geneste et al., Phys. Chem. Chem. Phys., 2015, 17, 19104]. In this previous work, we described, on the basis of density-functional calculations, proton transport in the classical and semi-classical regimes, and provided arguments in favor of an adiabatic picture for proton transfer at low temperature. We re-explain here our article (with more detail and precision), the content of which has been distorted in the Comment, and reiterate our arguments in this reply. We refute all criticisms. They are completely wrong in the context of our article. Even though a few of them are based on considerations probably true in some metals, they make no sense here since they do not correspond to the content of our work. It has not been understood in the Comment that two competitive configurations, associated with radically different transfer mechanisms, have been studied in our work. It has also not been understood in the Comment that the adiabatic regime described for transfer occurs in the protonic ground state, in a very-low barrier configuration with the protonic ground state energy larger than the barrier. Serious confusion has been made in the Comment with the case of H in metals like Nb or Ta, leading to the introduction of the notion of (protonic) "excited-state proton transfer", relevant for H in some metals, but (i) that does not correspond to the (ground state) adiabatic transfers here described, and (ii) that does not correspond to what is commonly described as the "adiabatic limit for proton transfer" in the scientific literature. We emphasize, accordingly, the large differences between proton transfer in the present oxide and hydrogen jumps in metals like Nb or Ta, and the similarities between proton transfer in the present oxide and in acid-base solutions. We finally describe a scenario for proton transfer in the present oxide regardless of the temperature regime.

Photostriction in Ferroelectrics from Density Functional Theory.

An ab initio procedure allowing the computation of the deformation of ferroelectric-based materials under light is presented. This numerical scheme consists in structurally relaxing the system under the constraint of a fixed n_{e} concentration of electrons photoexcited into a specific conduction band edge state from a chosen valence band state, via the use of a constrained density functional theory method. The resulting change in lattice constant along a selected crystallographic direction is then calculated for a reasonable estimate of n_{e}. This method is applied to bulk multiferroic BiFeO_{3} and predicts a photostriction effect of the same order of magnitude than the ones recently observed. A strong dependence of photostrictive response on both the reached conduction state and the crystallographic direction (along which this effect is determined) is also revealed. Furthermore, analysis of the results demonstrates that the photostriction mechanism mostly originates from the screening of the spontaneous polarization by the photoexcited electrons in combination with the inverse piezoelectric effect.

Simulating the Radio-Frequency Dielectric Response of Relaxor Ferroelectrics: Combination of Coarse-Grained Hamiltonians and Kinetic Monte Carlo Simulations.

The radio-frequency dielectric response of the lead-free Ba(Zr_{0.5}Ti_{0.5})O_{3} relaxor ferroelectric is simulated using a coarse-grained Hamiltonian. This concept, taken from real-space renormalization group theories, allows us to depict the collective behavior of correlated local modes gathered in blocks. Free-energy barriers for their thermally activated collective hopping are deduced from this ab initio-based approach, and used as input data for kinetic Monte Carlo simulations. The resulting numerical scheme allows us to simulate the dielectric response for external field frequencies ranging from kHz up to a few tens of MHz for the first time and to demonstrate, e.g., that local (electric or elastic) random fields lead to the dielectric relaxation in the radio-frequency range that has been observed in relaxors.

Photovoltaics with Ferroelectrics: Current Status and Beyond.

Ferroelectrics carry a switchable spontaneous electric polarization. This polarization is usually coupled to strain, making ferroelectrics good piezoelectrics. When coupled to magnetism, they become so-called multiferroic systems, a field that has been widely investigated since 2003. While ferroelectrics are birefringent and non-linear optically transparent materials, the coupling of polarization with optical properties has received, since 2009, renewed attention, triggered notably by low-bandgap ferroelectrics suitable for sunlight spectrum absorption and original photovoltaic effects. Consequently, power conversion efficiencies up to 8.1% were recently achieved and values of 19.5% were predicted, making photoferroelectrics promising photovoltaic alternatives. This article aims at providing an up-to-date review on this emerging and rapidly progressing field by highlighting several important issues and parameters, such as the role of domain walls, ways to tune the bandgap, consequences arising from the polarization switchability, and the role of defects and contact electrodes, as well as the downscaling effects. Beyond photovoltaicity, other polarization-related processes are also described, like light-induced deformation (photostriction) or light-assisted chemical reaction (photostriction). It is hoped that this overview will encourage further avenues to be explored and challenged and, as a byproduct, will inspire other research communities in material science, e.g., so-called hybrid halide perovskites.

Proton transport in barium stannate: classical, semi-classical and quantum regimes.

Density-functional theory calculations are performed to investigate proton transport in BaSnO3. Structural optimizations in the stable and saddle point configurations for transfer (hopping) and reorientation allow description of the high-temperature classical and semi-classical regimes, in which diffusion occurs by over-barrier motion. At lower temperature (typically below 300 K), we describe the thermally-assisted quantum regime, in which protonic motion is of quantum nature and occurs in "coincidence" configurations favored by thermal fluctuations of the surrounding atoms. Both the non-adiabatic and the adiabatic limits are examined. In the adiabatic limit, the protonic energy landscape in the coincidence configuration is very flat. Path-integral molecular dynamics simulations of the proton in the coincidence potential reveal, in the transfer case, that the density of probability of H(+) has its maximum at the saddle point, because the zero-point energy exceeds the coincidence barrier. Arguments are given that support the adiabatic picture for the transfer mechanism. In the case of reorientation, the time scales for the existence of the coincidence and for protonic motion, as estimated from the time-energy uncertainty principle by using a simple one-dimensional model, are of the same order of magnitude, suggesting that the adiabatic limit is not reached. Protonic transfer and reorientation in this oxide are therefore governed by different mechanisms below room temperature.

New iron hydrides under high pressure.

The Fe-H system has been investigated by combined x-ray diffraction studies and total energy calculations at pressures up to 136 GPa. The experiments involve laser annealing of hydrogen-embedded iron in a diamond anvil cell. Two new FeHx compounds, with x∼2 and x=3, are discovered at 67 and 86 GPa, respectively. Their crystal structures are identified (unit cell and Fe positional parameters from x-ray diffraction, H positional parameters from ab initio calculations) as tetragonal with space group I4/mmm for FeH(∼2) and as simple cubic with space group Pm3m for FeH3. Large metastability regimes are observed that allowed to measure the P(V) equation of state at room temperature of FeH, FeH(∼2), and FeH3.

A model for multiphoton absorption in dielectric materials induced by short laser pulses at moderate intensities.

We present a semi-analytical model for free electron production induced by multiphoton ionization in dielectric materials for short laser pulses at moderate intensities. Within this approach, the laser-induced absorption is described through the Bloch-Volkov formalism, and the electronic structure of materials is evaluated through first-principles calculations. Results obtained for NaCl and KDP (KH2PO4) materials show that significant deviations from the parabolic band approximation may occur. When the laser intensity increases, high multiphotonic orders may become the predominant mechanisms outside the centre of the Brillouin zone.

Strong isotope effect in phase II of dense solid hydrogen and deuterium.

Quantum nuclear zero-point motions in solid H(2) and D(2) under pressure are investigated at 80 K up to 160 GPa by first-principles path-integral molecular dynamics calculations. Molecular orientations are well defined in phase II of D(2), while solid H(2) exhibits large and very asymmetric angular quantum fluctuations in this phase, with possible rotation in the (bc) plane, making it difficult to associate a well-identified single classical structure. The mechanism for the transition to phase III is also described. Existing structural data support this microscopic interpretation.

Novel complex phenomena in ferroelectric nanocomposites.

A first-principles-based effective Hamiltonian is used to investigate finite-temperature properties of ferroelectric nanocomposites made of periodic arrays of ferroelectric nanowires embedded in a matrix formed by another ferroelectric material. Novel transitions and features related to flux-closure configurations are found. Examples include (i) a vortex core transition, that is characterized by the change of the vortex cores from being axisymmetric to exhibiting a 'broken symmetry'; (ii) translational mode of the vortex cores; (iii) striking zigzag dipolar chains along the vortex core axis; and (iv) phase-locking of ferroelectric vortices accompanied by ferroelectric antivortices. These complex phenomena are all found to coexist with a spontaneous electrical polarization aligned along the normal of the plane containing the vortices.

Polarization dependent chemistry of ferroelectric BaTiO3(001) domains.

Recent works suggest that the surface chemistry, in particular the presence of oxygen vacancies, can affect the polarization in a ferroelectric material. This should, in turn, influence the domain ordering driven by the need to screen the depolarizing field. Here we show using density-functional theory that the presence of oxygen vacancies at the surface of BaTiO(3)(001) preferentially stabilizes an inward pointing, P-, polarization. Mirror electron microscopy measurements of the domain ordering confirm the theoretical results.

Correlations and local order parameter in the paraelectric phase of barium titanate.

General features of the order parameter distribution in barium titanate in its paraelectric phase and in its ferroelectric phases (tetragonal and orthorhombic) are presented. The density of probability of the polarization [Formula: see text], defined by an average of the local order parameters over regions of various sizes and shapes (L(x) × L(y) × L(z)), is examined by molecular dynamics simulations using a first-principles derived effective Hamiltonian. The free energies [Formula: see text] associated with these probabilities are computed by thermodynamic integration. The evolution of these quantities are explained through the computation of pair correlations, which are found, as stated in several previous works, very anisotropic, 'needle-like', with longitudinal correlations ([Formula: see text]) having much longer range than transverse ones ([Formula: see text]). The correlations explain why the density of probability of the order parameter evolves from a multiple-peaked distribution with maxima along [111] (in the single cell), along [100] for small needle-like regions, towards a single-peaked distribution for larger regions. A useful expression in which the shape-dependence of the free energy is manifest is provided.

Thermodynamics and kinetics of the Schottky defect at terraces and steps on the MgO(001) surface.

The Schottky defects at both the flat MgO(001) surface and the monatomic-step edge have been investigated by equilibrium molecular dynamics simulations. The formation enthalpy as a function of the distance between the Mg and O vacancies that form a Schottky defect have been calculated and discussed. We conclude that a step edge is a stable location for a vacancy. The migration mechanism has been elucidated and an intermediate state has been identified. The associated activation enthalpies have been determined in the 700-1100 K temperature range. Both magnesium and oxygen vacancies at the surface are very mobile and can play a role during the crystal growth.

Atomistic screening mechanism of ferroelectric surfaces: an in situ study of the polar phase in ultrathin BaTiO3 films exposed to H2O.

The polarization screening mechanism and ferroelectric phase stability of ultrathin BaTiO(3) films exposed to water molecules is determined by first principles theory and in situ experiment. Surface crystallography data from electron diffraction combined with density functional theory calculations demonstrate that small water vapor exposures do not affect surface structure or polarization. Large exposures result in surface hydroxylation and rippling, formation of surface oxygen vacancies, and reversal of the polarization direction. Understanding interplay between ferroelectric phase stability, screening, and atomistic processes at surfaces is a key to control low-dimensional ferroelectricity.

Competing mechanisms in the atomic diffusion of a MgO admolecule on the MgO(001) surface.

The diffusion mechanism of a MgO admolecule on a flat MgO(001) surface has been investigated by equilibrium molecular dynamics simulation. Care has been taken in the choice of the phenomenological interionic potential used. Four distinct mechanisms have been found and the corresponding dynamical barriers determined at high temperature. Some static barriers have also been computed for comparison and all intermediate configurations have been obtained with the same phenomenological potential and also by the DFT-GGA approach. The hopping mechanisms involving the Mg adatom, although dominant, must be combined with the infrequent mechanisms involving displacements of O adatoms in order to provide the mass transport on the surface, which is crucial for crystal growth both in the nucleation and step-flow regimes.