Martensitic transformations in nanoscaled shape-memory alloys exhibit characteristic features absent for the bulk counterparts. Detailed understanding is required for applications in micro- and nanoelectromechanical systems, and experimental limitations render atomistic simulation an important complementary approach. Using a recently developed, accurate potential we investigate the phase transformation in freestanding Ni-Ti shape-memory nanoparticles with molecular-dynamics simulations. The results confirm that the decrease in the transformation temperature with decreasing particle size is correlated with an overstabilization of the austenitic surface energy over the martensitic surface energy. However, a detailed atomistic analysis of the nucleation and growth behavior reveals an unexpected difference in the mechanisms determining the austenite finish and martensite start temperature. While the austenite finish temperature is directly affected by a contribution of the surface energy difference, the martensite start temperature is mostly affected by the transformation strain, contrary to general expectations. This insight not only explains the reduced transformation temperature but also the reduced thermal hysteresis in freestanding nanoparticles.

The in-plane dc conductivity of twisted bilayer graphene is calculated using an expansion of the real-space Kubo-Bastin conductivity in terms of Chebyshev polynomials. We investigate within a tight-binding approach the transport properties as a function of rotation angle, applied perpendicular electric field, and vacancy disorder. We find that for high-angle twists, the two layers are effectively decoupled, and the minimum conductivity at the Dirac point corresponds to double the value observed in monolayer graphene. This remains valid even in the presence of vacancies, hinting that chiral symmetry is still preserved. On the contrary, for low twist angles, the conductivity at the Dirac point depends on the twist angle and is not protected in the presence of disorder. Furthermore, for low angles and in the presence of an applied electric field, we find that the chiral boundary states emerging between AB and BA regions contribute to the dc conductivity, despite the appearance of localized states in the AA regions. The results agree qualitatively with recent transport experiments in low-angle twisted bilayer graphene.

We report here a course of basic research into the potential suitability of a pseudo-icosahedral Cr aluminide as a material for high-temperature protective coatings. ${\mathrm{Cr}}_{55}{\mathrm{Al}}_{232-\delta }\mathrm{[}\delta =2.70\left(6\right)]$ exhibits high hardness at room temperature as well as low thermal conductivity and excellent oxidation resistance at 973 K, with an oxidation rate comparable to those of softer, denser benchmark materials. The origin of these promising properties can be traced to competing long-range and short-range symmetries within the pseudo-icosahedral crystal structure, suggesting new criteria for future materials research.

The generation of anti-Frenkel pairs (oxygen vacancies and oxygen interstitials) in monoclinic and cubic ${\mathrm{HfO}}_2$ under an applied electric field is examined. A thermodynamic model is used to derive an expression for the critical field strength required to generate an anti-Frenkel pair. The critical field strength of ${\mathcal{E}}_{\mathrm{aF}}^{\mathrm{cr}}\sim {10}^1{\mathrm{GVm}}^{-1}$ obtained for ${\mathrm{HfO}}_2$ exceeds substantially the field strengths routinely employed in the forming and switching operations of resistive switching ${\mathrm{HfO}}_2$ devices, suggesting that field-enhanced defect generation is negligible. Atomistic simulations with molecular static (MS) and molecular dynamic (MD) approaches support this finding. The MS calculations indicated a high formation energy of $\mathrm{\Delta }{E}_{\mathrm{aF}}\approx 8\mathrm{eV}$ for the infinitely separated anti-Frenkel pair, and only a decrease to $\mathrm{\Delta }{E}_{\mathrm{aF}}\approx 6\mathrm{eV}$ for the adjacent anti-Frenkel pair. The MD simulations showed no defect generation in either phase for $\mathcal{E}<3{\mathrm{GVm}}^{-1}$, and only sporadic defect generation in the monoclinic phase (at $\mathcal{E}=3{\mathrm{GVm}}^{-1})$ with fast $\left(t_{\mathrm{rec}}<4\mathrm{ps}\right)$ recombination. At even higher $\mathcal{E}$ but below ${\mathcal{E}}_{\mathrm{aF}}^{\mathrm{cr}}$ both monoclinic and cubic structures became unstable as a result of field-induced deformation of the ionic potential wells. Further MD investigations starting with preexisting anti-Frenkel pairs revealed recombination of all pairs within $t_{\mathrm{rec}}<1\mathrm{ps}$, even for the case of neutral vacancies and charged interstitials, for which formally there is no electrostatic attraction between the defects. In conclusion, we find no physically reasonable route to generating point-defects in ${\mathrm{HfO}}_2$ by an applied field.

A stochastic cumulant $GW$ method is presented, allowing us to map the evolution of photoemission spectra, quasiparticle energies, lifetimes, and emergence of collective excitations from molecules to bulklike systems with up to thousands of valence electrons, including Si nanocrystals and nanoplatelets. The quasiparticle energies rise due to their coupling with collective shake-up (plasmon) excitations, and this coupling leads to significant spectral weight loss (up to 50% for the low-energy states), shortening the lifetimes and shifting the spectral features to lower energies by as much as 0.6 eV. Such features are common to all the systems studied irrespective of their sizes and shapes. For small and low-dimensional systems the surface plasmon resonances affect the frequency of the collective excitation and position of the satellites.

We present an approach to calculate the optical absorption spectra that combines the quasiparticle self-consistent $\mathit{GW}$ method [Phys. Rev. B 76, 165106 (2007)] for the electronic structure with the solution of the ladder approximation to the Bethe-Salpeter equation for the macroscopic dielectric function. The solution of the Bethe-Salpeter equation has been implemented within an all-electron framework, using a linear muffin-tin orbital basis set, with the contribution from the nonlocal self-energy to the transition dipole moments (in the optical limit) evaluated explicitly. This approach addresses those systems whose electronic structure is poorly described within the standard perturbative $\mathit{GW}$ approaches with density-functional theory calculations as a starting point. The merits of this approach have been exemplified by calculating optical absorption spectra of a strongly correlated transition metal oxide, NiO, and a narrow gap semiconductor, Ge. In both cases, the calculated spectrum is in good agreement with the experiment. It is also shown that for systems whose electronic structure is well-described within the standard perturbative $\mathit{GW}$, such as Si, LiF, and $h\text{−}\mathrm{BN}$, the performance of the present approach is in general comparable to the standard $\mathit{GW}$ plus Bethe-Salpeter equation. It is argued that both vertex corrections to the electronic screening and the electron-phonon interaction are responsible for the observed systematic overestimation of the fundamental band gap and spectrum onset.

Using the ab initio evolutionary algorithm (implemented in uspex) and electronic structure calculations we investigate the properties of a new thermoelectric material FeSbAs, which is a material analog of the enigmatic thermoelectric ${\mathrm{FeSb}}_2$. We utilize the density functional theory and the Gutzwiller method to check the energetics. We find that FeSbAs can be made thermodynamically stable above $\sim 30$ GPa. We investigate the electronic structure and thermoelectric properties of FeSbAs based on the density functional theory and compare with those of ${\mathrm{FeSb}}_2$. Above 50 K, FeSbAs has higher Seebeck coefficients than ${\mathrm{FeSb}}_2$. Upon doping, the figure of merit becomes larger for FeSbAs than for ${\mathrm{FeSb}}_2$. Another material analog FeSbP, was also investigated, and found thermodynamically unstable even at very high pressure. Regarding ${\mathrm{FeSb}}_2$ as a member of a family of compounds $({\mathrm{FeSb}}_2$, FeSbAs, and FeSbP) we elucidate what are the chemical handles that control the gaps in this series. We also investigate solubility (As or P for Sb in ${\mathrm{FeSb}}_2)$ we found As to be more soluble. Finally, we study a two-band model for thermoelectric properties and find that the temperature dependent chemical potential and the presence of the ionized impurities are important to explain the extremum in the Seebeck coefficient exhibited in experiments for ${\mathrm{FeSb}}_2$.

Molecular dynamics simulations are used to analyze shock propagation in amorphous and crystalline polyethylene. Results for the shock velocity $U_s$ are compared to predictions from Pastine's equation of state and hydrostatic theory. The results agree with Pastine at high impact velocities. At low velocities the yield stress becomes important, increasing the shock velocity and leading to anisotropy in the crystalline response. Detailed analysis of changes in atomic order reveals the origin of the anisotropic response. For shock along the polymer backbone, an elastic front is followed by a plastic front where chains buckle with a characteristic wavelength. Shock perpendicular to the chain backbone can produce plastic deformation or transitions to different orthorhombic or monoclinic structures, depending on the impact speed and direction. Tensile loading does not produce stable shocks: Amorphous systems craze and fracture while for crystals the front broadens linearly with time.

Polyamide nanomembranes are at the heart of water desalination, a process which plays a critical role in clean water production. Improving their efficiency requires a better understanding of the relationship between chemistry, network structure, and performance but few techniques afford compositional information in ultrathin films $(<100$ nm). Here, we leverage resonant soft x-ray reflectivity, a measurement that is sensitive to the specific chemical bonds in organic materials, to quantify the functional group concentration in these polyamides. We first employ reference materials to establish quantitative relationships between changes in the optical constants and functional group density, and then use the results to evaluate the functional group concentrations of polyamide nanomembranes. We demonstrate that the difference in the amide carbonyl and carboxylic acid group concentrations can be used to calculate the crosslink density, which is shown to vary significantly across three different polyamide chemistries. A clear relationship is established between the functional group density and the permselectivity $\left(\alpha \right)$, indicating that more densely crosslinked materials result in a higher $\alpha$ of the nanomembranes. Finally, measurements on a polyamide/poly(acrylic acid) bilayer demonstrate the ability of this approach to quantify depth-dependent functional group concentrations in thin films.

We present a multiphase-field model to describe quantitatively nanowire growth by the vapor-liquid-solid (VLS) process. The free-energy functional of this model depends on three nonconserved order parameters that distinguish the vapor, liquid, and solid phases and describe the energetic properties of various interfaces, including arbitrary forms of anisotropic $\gamma$ plots for the solid-vapor and solid-liquid interfaces. The evolution equations for those order parameters describe basic kinetic processes including the rapid (quasi-instantaneous) equilibration of the liquid catalyst to a droplet shape with constant mean curvature, the slow incorporation of growth atoms at the droplet surface, and crystallization within the droplet. The standard constraint that the sum of the phase fields equals unity and the conservation of the number of catalyst atoms, which relates the catalyst volume to the concentration of growth atoms inside the droplet, are handled via separate Lagrange multipliers. An analysis of the model is presented that rigorously maps the phase-field equations to a desired set of sharp-interface equations for the evolution of the phase boundaries under the constraint of force balance at three-phase junctions (triple points) given by the Young-Herring relation that includes torque term related to the anisotropy of the solid-liquid and solid-vapor interface excess free energies. Numerical examples of growth in two dimensions are presented for the simplest case of vanishing crystalline anisotropy and the more realistic case of a solid-liquid $\gamma$ plot with cusped minima corresponding to two sets of $\left(10\right)$ and $\left(11\right)$ facets. The simulations reproduce many of the salient features of nanowire growth observed experimentally, including growth normal to the substrate with tapering of the side walls, transitions between different growth orientations, and crawling growth along the substrate. They also reproduce different observed relationships between the nanowire growth velocity and radius depending on the growth condition. For the basic normal growth mode, the steady-state solid-liquid interface tip shape consists of a main facet intersected by two truncated side facets ending at triple points. The ratio of truncated and main facet lengths are in quantitative agreement with the prediction of sharp-interface theory that is developed here for faceted nanowire growth in two dimensions.

Graphene exhibits a nonequidistant Landau quantization with tunable Landau-level (LL) transitions in the technologically desired terahertz spectral range. Here, we present a strategy for an electrically driven terahertz laser based on Landau-quantized graphene as the gain medium. Performing microscopic modeling of the coupled electron, phonon, and photon dynamics in such a laser, we reveal that an inter-LL population inversion can be achieved resulting in the emission of coherent terahertz radiation. The presented paper provides a concrete recipe for the experimental realization of tunable graphene-based terahertz laser systems.

This work investigates the feasibility of electrical valley filtering for holes in transition metal dichalcogenides. We look specifically into the scheme that utilizes a potential barrier to produce valley-dependent tunneling rates, and perform the study with both a $k·p$-based analytic method and a recursive Green's function–based numerical method. The study yields the transmission coefficient as a function of incident energy and transverse wave vector, for holes going through lateral quantum barriers oriented in either armchair or zigzag directions, in both homogeneous and heterogeneous systems. The main findings are the following: (1) The tunneling current valley polarization increases with increasing barrier width or height; (2) both the valley-orbit interaction and band structure warping contribute to valley-dependent tunneling, with the former contribution being manifest in structures with asymmetric potential barriers, and the latter being orientation dependent and reaching maximum for transmission in the armchair direction; and (3) for transmission $\sim 0.1$, a tunneling current valley polarization of the order of $10\%$ can be achieved.

Oxygen vacancies at ceria $\left(\mathrm{Ce}{\mathrm{O}}_2\right)$ surfaces play an essential role in catalytic applications. However, during the past decade, the near-surface vacancy structures at $\mathrm{Ce}{\mathrm{O}}_2\left(111\right)$ have been questioned due to the contradictory results from experiments and theoretical simulations. Whether surface vacancies agglomerate, and which is the most stable vacancy structure for varying vacancy concentration and temperature, are being heatedly debated. By combining density functional theory calculations and Monte Carlo simulations, we proposed a unified model to explain all conflicting experimental observations and theoretical results. We find a novel trimeric vacancy structure which is more stable than any other one previously reported, which perfectly reproduces the characteristics of the double linear surface oxygen vacancy clusters observed by STM. Monte Carlo simulations show that at low temperature and low vacancy concentrations, vacancies prefer subsurface sites with a local (2 × 2) ordering, whereas mostly linear surface vacancy clusters do form with increased temperature and degree of reduction. These results well explain the disputes about the stable vacancy structure and surface vacancy clustering at $\mathrm{Ce}{\mathrm{O}}_2\left(111\right)$, and provide a foundation for the understanding of the redox and catalytic chemistry of metal oxides.

Single-crystal Heusler atomic-scale superlattices that have been predicted to exhibit perpendicular magnetic anisotropy and half-metallicity have been successfully grown by molecular beam epitaxy. Superlattices consisting of full-Heusler ${\mathrm{Co}}_2\mathrm{MnAl}$ and ${\mathrm{Fe}}_2\mathrm{MnAl}$ with one- to three-unit-cell periodicity were grown on GaAs (001), MgO (001), and Cr (001)/MgO (001). Electron-energy-loss spectroscopy maps confirmed clearly segregated epitaxial Heusler layers with high cobalt or high iron concentrations for samples grown near room temperature on GaAs (001). Superlattice structures grown with an excess of aluminum had significantly lower thin-film shape anisotropy and resulted in an out-of-plane spin reorientation transition at temperatures below 200 K for samples grown on GaAs (001). Synchrotron-based spin-resolved photoemission spectroscopy found that the superlattice structure improves the Fermi-level spin polarization near the $X$ point in the bulk Brillouin zone. Stoichiometric ${\mathrm{Co}}_2\mathrm{MnAl}$ terminated superlattice grown on MgO (001) had a spin polarization of 95%, while a pure ${\mathrm{Co}}_2\mathrm{MnAl}$ film had a spin polarization of only 65%.

Tantalum pentoxide $\left(\mathrm{T}{\mathrm{a}}_2{\mathrm{O}}_5\right)$ is a wide-gap semiconductor which has important technological applications. Despite the enormous efforts from both experimental and theoretical studies, the ground-state crystal structure of $\mathrm{T}{\mathrm{a}}_2{\mathrm{O}}_5$ is not yet uniquely determined. Based on first-principles calculations in combination with evolutionary algorithm, we identify a triclinic phase of $\mathrm{T}{\mathrm{a}}_2{\mathrm{O}}_5$, which is energetically much more stable than any phases or structural models reported previously. Characterization of the static and dynamical properties of the phase reveals the common features shared with previous metastable phases of $\mathrm{T}{\mathrm{a}}_2{\mathrm{O}}_5$. In particular, we show that the $d$ spacing of $\sim 3.8\AA$ found in the x-ray diffraction patterns of many previous experimental works is actually the radius of the second Ta-Ta coordination shell as defined by radial distribution functions.

We address the role of nonlocal Coulomb correlations and short-range magnetic fluctuations in the high-temperature phase of ${\mathrm{Sr}}_2{\mathrm{IrO}}_4$ within state-of-the-art spectroscopic and first-principles theoretical methods. Introducing an “oriented-cluster dynamical mean-field scheme”, we compute momentum-resolved spectral functions, which we find to be in excellent agreement with angle-resolved photoemission spectra. We show that while short-range antiferromagnetic fluctuations are crucial to accounting for the electronic properties of ${\mathrm{Sr}}_2{\mathrm{IrO}}_4$ even in the high-temperature paramagnetic phase, long-range magnetic order is not a necessary ingredient of the insulating state. Upon doping, an exotic metallic state is generated, exhibiting cuprate-like pseudo-gap spectral properties, for which we propose a surprisingly simple theoretical mechanism.

The electronic structure and optical properties of yttria-stabilized zirconia are investigated as a function of the yttria content using multiple experimental and theoretical methods, including electron energy-loss spectroscopy, Kramers-Kronig analysis to obtain the optical parameters, photoelectron spectroscopy, and density functional theory. It is shown that many properties, including the band gaps, the crystal field splitting, the so-called defect gap between acceptor $\left({\mathrm{Y}}_{\mathrm{Zr}}^{{}^{\prime }}\right)$ and donor $\left({\mathrm{V}}_{\mathrm{O}}^{••}\right)$ states, as well as the index of refraction in the visible range exhibit the same “zig-zag-like” trend as the unit cell height does, showing the influence of an increased yttria content as well as of the tetragonal–cubic phase transition between $8\mathrm{mol}\%$ and $20\mathrm{mol}\%{\mathrm{Y}}_2{\mathrm{O}}_3$. Also, with Čerenkov spectroscopy (CS), a new technique is presented, providing information complementary to electron energy-loss spectroscopy. In CS, the Čerenkov radiation emitted inside the TEM is used to measure the onset of optical absorption. The apparent absorption edges in the Čerenkov spectra correspond to the energetic difference between the disorder states close to the valence band and the oxygen-vacancy-related electronic states within the band gap. Theoretical computations corroborate this assignment: they find both, the acceptor states and the donor states, at the expected energies in the band structures for diverse yttria concentrations. In the end, a schematic electronic structure diagram of the area around the band gap is constructed, including the chemical potential of the electrons obtained from photoelectron spectroscopy. The latter reveal that tetragonal YSZ corresponds to a $p$-type semiconductor, whereas the cubic samples exhibit $n$-type semiconductor properties.

Single-layer and bilayer carbon and hexagonal boron nitride nanoscrolls as well as nanoscrolls made of bilayer graphene/hexagonal boron nitride heterostructure are considered. Structures of stable states of the corresponding nanoscrolls prepared by rolling single-layer and bilayer rectangular nanoribbons are obtained based on the analytical model and numerical calculations. The lengths of nanoribbons for which stable and energetically favorable nanoscrolls are possible are determined. Barriers to rolling of single-layer and bilayer nanoribbons into nanoscrolls and barriers to nanoscroll unrolling are calculated. Based on the calculated barriers nanoscroll lifetimes in the stable state are estimated. Elastic constants for bending of graphene and hexagonal boron nitride layers used in the model are found by density functional theory calculations.

Interfaces play a crucial role in the study of novel phenomena emerging at heterostructures comprising metals and functional oxides. For this reason, attention should be paid to the interface chemistry, which can favor the interdiffusion of atomic species and, under certain conditions, lead to the formation of radically different compounds with respect to the original constituents. In this work, we consider Cr/$\mathrm{BaTi}{\mathrm{O}}_3$ heterostructures grown on $\mathrm{SrTi}{\mathrm{O}}_3$ (100) substrates. Chromium thin films (1–2 nm thickness) are deposited by molecular beam epitaxy on the $\mathrm{BaTi}{\mathrm{O}}_3$ layer, and subsequently annealed in vacuum at temperatures ranging from 473 to 773 K. A disordered metallic layer is detected for annealing temperatures up to 573 K, whereas, at higher temperatures, we observe a progressive oxidation of chromium, which we relate to the thermally activated migration of oxygen from the substrate. The chromium oxidation state is $+3$ and the film shows a defective rocksalt structure, which grows lattice matched on the underlying $\mathrm{BaTi}{\mathrm{O}}_3$ layer. One out of every three atoms of chromium is missing, producing an uncommon tetragonal phase with $\mathrm{C}{\mathrm{r}}_2{\mathrm{O}}_3$ stoichiometry. Despite the structural difference with respect to the ordinary corundum α-$\mathrm{C}{\mathrm{r}}_2{\mathrm{O}}_3$ phase, we demonstrate both experimentally and theoretically that the electronic properties of the two phases are, to a large extent, equivalent.

The reduction of dimensionality is considered an efficient pathway to boost the performances of thermoelectric materials. Quantum confinement of the carriers is expected to induce large Seebeck coefficients $\left(S\right)$ and it also suppresses the thermal conductivity by increasing the phonon scattering processes. However, quantum confinement in superlattices is not always easy to achieve and needs to be carefully validated. In the past decade, large values of $S$ have been measured in $\left({\mathrm{SrTiO}}_3\right)$/$\left({\mathrm{SrTi}}_{0.8}{\mathrm{Nb}}_{0.2}{\mathrm{O}}_3\right)$ superlattices [H. Ohta et al., Nat. Mater. 6, 129 (2007); Y. Mune et al., Appl. Phys. Lett. 91, 192105 (2007)]. In the $\delta$-doped compound, the reported $S$ was almost six times larger than that of the bulk material. This huge increase has been attributed to the two-dimensional carrier confinement in the doped regions. Here, we demonstrate that the experimental data are well explained quantitatively assuming delocalized electrons in both in-plane and growth directions. Moreover, we rule out the confined electron hypothesis whose signature would be the suppression of the Seebeck coefficient. This strongly suggests that the presupposed confinement picture in these superlattices is unlikely.