In-Plane Flexoelectricity in Two-Dimensional D_{3d} Crystals.

We predict a large in-plane polarization response to bending in a broad class of trigonal two-dimensional crystals. We define and compute the relevant flexoelectric coefficients from first principles as linear-response properties of the undistorted layer by using the primitive crystal cell. The ensuing response (evaluated for SnS_{2}, silicene, phosphorene, and RhI_{3} monolayers and for a hexagonal BN bilayer) is up to 1 order of magnitude larger than the out-of-plane components in the same material. We illustrate the topological implications of our findings by calculating the polarization textures that are associated with a variety of rippled and bent structures. We also determine the longitudinal electric fields induced by a flexural phonon at leading order in amplitude and momentum.

Accurate Prediction of Hall Mobilities in Two-Dimensional Materials through Gauge-Covariant Quadrupolar Contributions.

Despite considerable efforts, accurate computations of electron-phonon and carrier transport properties of low-dimensional materials from first principles have remained elusive. By building on recent advances in the description of long-range electrostatics, we develop a general approach to the calculation of electron-phonon couplings in two-dimensional materials. We show that the nonanalytic behavior of the electron-phonon matrix elements depends on the Wannier gauge, but that a missing Berry connection restores invariance to quadrupolar order. We showcase these contributions in a MoS_{2} monolayer, calculating intrinsic drift and Hall mobilities with precise Wannier interpolations. We also find that the contributions of dynamical quadrupoles to the scattering potential are essential, and that their neglect leads to errors of 23% and 76% in the room-temperature electron and hole Hall mobilities, respectively.

Direct and Converse Flexoelectricity in Two-Dimensional Materials.

Building on recent developments in electronic-structure methods, we define and calculate the flexoelectric response of two-dimensional (2D) materials fully from first principles. In particular, we show that the open-circuit voltage response to a flexural deformation is a fundamental linear-response property of the crystal that can be calculated within the primitive unit cell of the flat configuration. Applications to graphene, silicene, phosphorene, boron nitride, and transition-metal dichalcogenide monolayers reveal that two distinct contributions exist, respectively of purely electronic and lattice-mediated nature. Within the former, we identify a key metric term, consisting in the quadrupolar moment of the unperturbed charge density. We propose a simple continuum model to connect our findings with the available experimental measurements of the converse flexoelectric effect.

Using High Multipolar Orders to Reconstruct the Sound Velocity in Piezoelectrics from Lattice Dynamics.

Information over the phonon band structure is crucial to predicting many thermodynamic properties of materials, such as thermal transport coefficients. Highly accurate phonon dispersion curves can be, in principle, calculated in the framework of density-functional perturbation theory. However, well-established techniques can run into trouble (or even catastrophically fail) in the case of piezoelectric materials, where the acoustic branches hardly reproduce the physically correct sound velocity. Here we identify the culprit in the higher-order multipolar interactions between atoms and demonstrate an effective procedure that fixes the aforementioned issue. Our strategy drastically improves the predictive power of perturbative lattice-dynamical calculations in piezoelectric crystals and is directly implementable for high-throughput generation of materials databases.

Electron-Phonon beyond Fröhlich: Dynamical Quadrupoles in Polar and Covalent Solids.

We include the treatment of quadrupolar fields beyond the Fröhlich interaction in the first-principles electron-phonon vertex in semiconductors. Such quadrupolar fields induce long-range interactions that have to be taken into account for accurate physical results. We apply our formalism to Si (nonpolar), GaAs, and GaP (polar) and demonstrate that electron mobilities show large errors if dynamical quadrupoles are not properly treated.

ABINIT: Overview and focus on selected capabilities.

abinit is probably the first electronic-structure package to have been released under an open-source license about 20 years ago. It implements density functional theory, density-functional perturbation theory (DFPT), many-body perturbation theory (GW approximation and Bethe-Salpeter equation), and more specific or advanced formalisms, such as dynamical mean-field theory (DMFT) and the "temperature-dependent effective potential" approach for anharmonic effects. Relying on planewaves for the representation of wavefunctions, density, and other space-dependent quantities, with pseudopotentials or projector-augmented waves (PAWs), it is well suited for the study of periodic materials, although nanostructures and molecules can be treated with the supercell technique. The present article starts with a brief description of the project, a summary of the theories upon which abinit relies, and a list of the associated capabilities. It then focuses on selected capabilities that might not be present in the majority of electronic structure packages either among planewave codes or, in general, treatment of strongly correlated materials using DMFT; materials under finite electric fields; properties at nuclei (electric field gradient, Mössbauer shifts, and orbital magnetization); positron annihilation; Raman intensities and electro-optic effect; and DFPT calculations of response to strain perturbation (elastic constants and piezoelectricity), spatial dispersion (flexoelectricity), electronic mobility, temperature dependence of the gap, and spin-magnetic-field perturbation. The abinit DFPT implementation is very general, including systems with van der Waals interaction or with noncollinear magnetism. Community projects are also described: generation of pseudopotential and PAW datasets, high-throughput calculations (databases of phonon band structure, second-harmonic generation, and GW computations of bandgaps), and the library libpaw. abinit has strong links with many other software projects that are briefly mentioned.

Phonon transport across crystal-phase interfaces and twin boundaries in semiconducting nanowires.

We combine state-of-the-art Green's-function methods and nonequilibrium molecular dynamics calculations to study phonon transport across the unconventional interfaces that make up crystal-phase and twinning superlattices in nanowires. We focus on two of their most paradigmatic building blocks: cubic (diamond/zinc blende) and hexagonal (lonsdaleite/wurtzite) polytypes of the same group-IV or III-V material. Specifically, we consider InP, GaP and Si, and both the twin boundaries between rotated cubic segments and the crystal-phase boundaries between different phases. We reveal the atomic-scale mechanisms that give rise to phonon scattering in these interfaces, quantify their thermal boundary resistance and illustrate the failure of common phenomenological models in predicting those features. In particular, we show that twin boundaries have a small but finite interface thermal resistance that can only be understood in terms of a fully atomistic picture.

Alkali-Activated Cements for TES Materials in Buildings' Envelops Formulated With Glass Cullet Recycling Waste and Microencapsulated Phase Change Materials.

Within the thermal energy storage field, one of the main challenges of this study is the development of new enhanced heat storage materials to be used in the building sector. The purpose of this study is the development of alkali-activated cements (AACs) with mechanical properties to store high amounts of heat. These AACs incorporate wastes from industrial glass process as well as microencapsulated phase change materials (mPCMs) to improve the thermal inertia of building walls, and accordingly respective energy savings. The research presented below consists of the exhaustive characterization of different AACs formulated from some waste generated during the proper management of municipal waste used as precursor. In this case study, AACs were formulated with the waste generated during the recycling of glass cullet, namely ceramic, stone, and porcelain (CSP), which is embedding a mPCM. The addition of mPCM was used as thermal energy storage (TES) material. The mechanical properties were also evaluated in order to test the feasibility of the use of the new formulated materials as a passive TES system. The results showed that the AAC obtained from CSP (precursors) mixed with mPCMs to obtain a thermal regulator material to be implemented in building walls was reached successfully. The material developed was resistant enough to perform as insulating panels. The formulated materials had high storage capacity depending on the PCM content. The durability of the mPCM shell was studied in contact with alkaline medium (NaOH 4 M) and no degradation was confirmed. Moreover, the higher the content of mPCM, the lower the mechanical properties expected, due to the porosity increments with mPCM incorporation in the formulations.

Tuning thermal transport in Si nanowires by isotope engineering.

We study thermal transport in isotopically disordered Si nanowires, discussing the feasibility of phonon engineering for thermoelectric applications within these systems. To this purpose, we carry out atomistic molecular dynamics and nonequilibrium Green's function calculations to characterize the dependence of the thermal conductance as a function of the isotope concentration, isotope radial distribution and temperature. We show that a reduction of the conductivity of up to 20% can be achieved with suitable isotope blends at room temperature and approximately 50% at low temperature. Interestingly, precise control of the isotope composition or radial distribution is not needed. An isotope disordered nanowire roughly behaves like a low-pass filter, as isotope impurities are transparent for long wave-length acoustic phonons, while only mid- and high-frequency optical phonons undergo significant scattering.

Tailoring the core electron density in modulation-doped core-multi-shell nanowires.

We show how a proper radial modulation of the composition of core-multi-shell nanowires (NWs) critically enhances the control of the free-carrier density in the high-mobility core with respect to core-single-shell structures, thus overcoming the technological difficulty of fine tuning the remote doping density. We calculate the electron population of the different NW layers as a function of the doping density and of several geometrical parameters by means of a self-consistent Schrödinger-Poisson approach: free carriers tend to localize in the outer shell and screen the core from the electric field of the dopants.