Connecting Higher-Order Topology with the Orbital Hall Effect in Monolayers of Transition Metal Dichalcogenides.

Monolayers of transition metal dichalcogenides (TMDs) in the 2H structural phase have been recently classified as higher-order topological insulators (HOTIs), protected by C_{3} rotation symmetry. In addition, theoretical calculations show an orbital Hall plateau in the insulating gap of TMDs, characterized by an orbital Chern number. We explore the correlation between these two phenomena in TMD monolayers in two structural phases: the noncentrosymmetric 2H and the centrosymmetric 1T. Using density functional theory, we confirm the characteristics of 2H TMDs and reveal that 1T TMDs are identified by a Z_{4} topological invariant. As a result, when cut along appropriate directions, they host conducting edge states, which cross their bulk energy-band gaps and can transport orbital angular momentum. Our linear response calculations thus indicate that the HOTI phase is accompanied by an orbital Hall effect. Using general symmetry arguments, we establish a connection between the two phenomena with potential implications for orbitronics and spin orbitronics.

Stability and Rupture of an Ultrathin Ionic Wire.

Using a combination of in situ high-resolution transmission electron microscopy and density functional theory, we report the formation and rupture of ZrO_{2} atomic ionic wires. Near rupture, under tensile stress, the system favors the spontaneous formation of oxygen vacancies, a critical step in the formation of the monatomic bridge. In this length scale, vacancies provide ductilelike behavior, an unexpected mechanical behavior for ionic systems. Our results add an ionic compound to the very selective list of materials that can form monatomic wires and they contribute to the fundamental understanding of the mechanical properties of ceramic materials at the nanoscale.

Machine Learning of Microscopic Ingredients for Graphene Oxide/Cellulose Interaction.

Understanding the role of microscopic attributes in nanocomposites allows one to control and, therefore, accelerate experimental system designs. In this work, we extracted the relevant parameters controlling the graphene oxide binding strength to cellulose by combining first-principles calculations and machine learning algorithms. We were able to classify the systems among two classes with higher and lower binding energies, which are well defined based on the isolated graphene oxide features. Using theoretical X-ray photoelectron spectroscopy analysis, we show the extraction of these relevant features. In addition, we demonstrate the possibility of refined control within a machine learning regression between the binding energy values and the system's characteristics. Our work presents a guiding map to control graphene oxide/cellulose interaction.

At the Verge of Topology: Vacancy-Driven Quantum Spin Hall in Trivial Insulators.

Vacancies in materials structure─lowering its atomic density─take the system closer to the atomic limit, to which all systems are topologically trivial. Here we show a mechanism of mediated interaction between vacancies inducing a topologically nontrivial phase. Within an ab initio approach we explore topological transition dependence with the vacancy density in transition metal dichalcogenides. As a case of study, we focus on the PtSe2, for which the pristine form is a trivial semiconductor with an energy gap of 1.2 eV. The vacancies states lead to a large topological gap of 180 meV within the pristine system gap. We derive an effective model describing this topological phase in other transition metal dichalcogenide systems. The mechanism driving the topological phase allows the construction of backscattering protected metallic channels embedded in a semiconducting host.

Room-Temperature Negative Differential Resistance in Surface-Supported Metal-Organic Framework Vertical Heterojunctions.

The advances of surface-supported metal-organic framework (SURMOF) thin-film synthesis have provided a novel strategy for effectively integrating metal-organic framework (MOF) structures into electronic devices. The considerable potential of SURMOFs for electronics results from their low cost, high versatility, and good mechanical flexibility. Here, the first observation of room-temperature negative differential resistance (NDR) in SURMOF vertical heterojunctions is reported. By employing the rolled-up nanomembrane approach, highly porous sub-15 nm thick HKUST-1 films are integrated into a functional device. The NDR is tailored by precisely controlling the relative humidity (RH) around the device and the applied electric field. The peak-to-valley current ratio (PVCR) of about two is obtained for low voltages (<2 V). A transition from a metastable state to a field emission-like tunneling is responsible for the NDR effect. The results are interpreted through band diagram analysis, density functional theory (DFT) calculations, and ab initio molecular dynamics simulations for quasisaturated water conditions. Furthermore, a low-voltage ternary inverter as a multivalued logic (MVL) application is demonstrated. These findings point out new advances in employing unprecedented physical effects in SURMOF heterojunctions, projecting these hybrid structures toward the future generation of scalable functional devices.

Conformational analysis of tannic acid: Environment effects in electronic and reactivity properties.

Polyphenols are natural molecules of crucial importance in many applications, of which tannic acid (TA) is one of the most abundant and established. Most high-value applications require precise control of TA interactions with the system of interest. However, the molecular structure of TA is still not comprehended at the atomic level, of which all electronic and reactivity properties depend. Here, we combine an enhanced sampling global optimization method with density functional theory (DFT)-based calculations to explore the conformational space of TA assisted by unsupervised machine learning visualization and then investigate its lowest energy conformers. We study the external environment's effect on the TA structure and properties. We find that vacuum favors compact structures by stabilizing peripheral atoms' weak interactions, while in water, the molecule adopts more open conformations. The frontier molecular orbitals of the conformers with the lowest harmonic vibrational free energy have a HOMO-LUMO energy gap of 2.21 (3.27) eV, increasing to 2.82 (3.88) eV in water, at the DFT generalized gradient approximation (and hybrid) level of theory. Structural differences also change the distribution of potential reactive sites. We establish the fundamental importance of accurate structural consideration in determining TA and related polyphenol interactions in relevant technological applications.

Ambipolar Resistive Switching in an Ultrathin Surface-Supported Metal-Organic Framework Vertical Heterojunction.

Memristors (MRs) are considered promising devices with the enormous potential to replace complementary metal-oxide-semiconductor (CMOS) technology, which approaches the scale limit. Efforts to fabricate MRs-based hybrid materials may result in suitable operating parameters coupled to high mechanical flexibility and low cost. Metal-organic frameworks (MOFs) arise as a favorable candidate to cover such demands. The step-by-step growth of MOFs structures on functionalized surfaces, called surface-supported metal-organic frameworks (SURMOFs), opens the possibility for designing new applications in strategic fields such as electronics, optoelectronics, and energy harvesting. However, considering the MRs architecture, the typical high porosity of these hybrid materials may lead to short-circuited devices easily. In this sense, here, it is reported for the first time the integration of SURMOF films in rolled-up scalable-functional devices. A freestanding metallic nanomembrane provides a robust and self-adjusted top mechanical contact on the SURMOF layer. The electrical characterization reveals an ambipolar resistive switching mediated by the humidity level with low-power consumption. The electronic properties are investigated with density functional theory (DFT) calculations. Furthermore, the device concept is versatile, compatible with the current parallelism demands of integration, and transcends the challenge in contacting SURMOF films for scalable-functional devices.

Ab Initio Simulations and Materials Chemistry in the Age of Big Data.

In this perspective, we discuss computational advances in the last decades, both in algorithms as well as in technologies, that enabled the development, widespread use, and maturity of simulation methods for molecular and materials systems. Such advances led to the generation of large amounts of data, which required the creation of several computational databases. Within this scenario, with the democratization of data access, the field now encounters several opportunities for data-driven approaches toward chemical and materials problems. Specifically, machine learning methods for predictions of novel materials or properties are being increasingly used with great success. However, black box usage fails in many instances; several technical details require expert knowledge in order for the predictions to be useful, such as with descriptors and algorithm selection. These approaches represent a direction for further developments, notably allowing advances for both developed and emerging countries with modest computational infrastructures.

Toward Realistic Amorphous Topological Insulators.

The topological properties of materials are, until now, associated with the features of their crystalline structure, although translational symmetry is not an explicit requirement of the topological phases. Recent studies of hopping models on random lattices have demonstrated that amorphous model systems show a nontrivial topology. Using ab initio calculations, we show that two-dimensional amorphous materials can also display topological insulator properties. More specifically, we present a realistic state-of-the-art study of the electronic and transport properties of amorphous bismuthene systems, showing that these materials are topological insulators. These systems are characterized by the topological index [Formula: see text]2 = 1 and bulk-edge duality, and their linear conductance is quantized, [Formula: see text], for Fermi energies within the topological gap. Our study opens the path to the experimental and theoretical investigation of amorphous topological insulator materials.

Spin-Polarization Control Driven by a Rashba-Type Effect Breaking the Mirror Symmetry in Two-Dimensional Dual Topological Insulators.

Three-dimensional topological insulators protected by both the time reversal (TR) and mirror symmetries were recently predicted and observed. Two-dimensional materials featuring this property and their potential for device applications have been less explored. We find that, in these systems, the spin polarization of edge states can be controlled with an external electric field breaking the mirror symmetry. This symmetry requires that the spin polarization is perpendicular to the mirror plane; therefore, the electric field induces spin-polarization components parallel to the mirror plane. Since this field preserves the TR topological protection, we propose a transistor model using the spin direction of protected edge states as a switch. In order to illustrate the generality of the proposed phenomena, we consider compounds protected by mirror planes parallel and perpendicular to the structure, e.g., Na_{3}Bi and half-functionalized (HF) hexagonal compounds, respectively. For this purpose, we first construct a tight-binding effective model for the Na_{3}Bi compound and predict that HF-honeycomb lattice materials are also dual topological insulators.

Electronic transport properties of MoS2 nanoribbons embedded in butadiene solvent.

Transition metal dichalcogenides (TMDCs) are promising materials for applications in nanoelectronics and correlated fields, where their metallic edge states play a fundamental role in the electronic transport. In this work, we investigate the transport properties of MoS2 zigzag nanoribbons under a butadiene (C4H6) atmosphere, as this compound has been used to obtain MoS2 flakes by exfoliation. We use density functional theory combined with non-equilibrium Green's function techniques, in a methodology contemplating disorder and different coverages. Our results indicate a strong modulation of the TMDC electronic transport properties driven by butadiene molecules anchored at their edges, producing the suppression of currents due to a backscattering process. Our results indicate a high sensitivity of the TMDC edge states. Thus, the mechanisms used to reduce the dimensionality of MoS2 considerably modify its transport properties.

Dynamic covalent bond from first principles: Diarylbibenzofuranone structural, electronic, and oxidation studies.

A structure that can self-heal under standard conditions is a challenge faced nowadays and is one of the most promising areas in smart materials science. This can be achieved by dynamic bonds, of which diarylbibenzofuranone (DABBF) dynamic covalent bond is an appealing solution. In this report, we studied the DABBF bond formation against arylbenzofuranone (ABF) and O2 reaction (autoxidation). Our results show that the barrierless DABBF bond formation is preferred over autoxidation due to the charge transfer process that results in the weakly bonded superoxide. We calculated the electronic and structural properties using total energy density functional theory. © 2017 Wiley Periodicals, Inc.

Nanodots of transition metal dichalcogenides embedded in MoS2 and MoSe2: first-principles calculations.

The energetic stability and the electronic properties of nanodots (NDs) composed of transition metal dichalcogenides, XS2 and XSe2 (with X = Mo, W and Nb) embedded in single layer MoS2 and MoSe2 hosts, were investigated based on first-principles calculations. We find that through a suitable combination of the ND and host materials it is possible to control the electron-hole localization. For instance, in NDs of WS2 in the MoS2 host we find the highest occupied (hole) states localized in the ND region, while the lowest unoccupied (electron) states spread out in the MoS2 host. On the other hand, by changing the ND and host materials, the electron states become localized in the MoS2 ND in the WS2 host. Further electronic structure calculations show that the NDs of NbS2 and NbSe2 give rise to a set of spin degenerate empty states within the energy gap of the MoS2 and MoSe2 hosts. The spin degeneracy can be removed by negatively charging the ND system. Such n-type doping was examined by considering a van der Waals (vdW) heterostructure composed of a graphene layer lying on the NbS2 and NbSe2 NDs. Indeed we found a net magnetic moment localized in the ND region.

Directional dependence of the electronic and transport properties of 2D borophene and borophane.

Very recently two dimensional layers of boron atoms, so called borophene, have been successfully synthesized. It presents a metallic band structure, with a strong anisotropic character. Upon further hydrogen adsorption a new material is obtained, borophane; giving rise to a Dirac cone structure like the one in graphene. We have performed a first-principles study of the electronic and transport properties of borophene and borophane through the Landauer-Büttiker formalism. We find that borophene presents an electronic current two orders of magnitude larger than borophane. In addition we verified the direction dependence of the electronic current in two perpendicular directions, namely, Ix and Iy; where for both systems, we found a current ratio, η = Ix/Iy, of around 2. Aiming to control such a current anisotropy, η, we performed a study of its dependence with respect to an external strain. Where, by stretching the borophane sheet, η increases by 11% for a bias voltage of 50 mV.

On the nature of the solvated electron in ice Ih.

The water-solvated excess electron (EE) is a key chemical agent whose hallmark signature, its asymmetric optical absorption spectrum, continues to be a topic of debate. While nearly all investigation has focused on the liquid-water solvent, the fact that the crystalline-water solvated EE shows a very similar visible absorption pattern has remained largely unexplored. Here, we present spin-polarized density-functional theory calculations subject to periodic boundary conditions of the interplay between an EE and a number of intrinsic lattice defects in ice Ih. Our results show that the optical absorption signatures in the presence of three unsaturated hydrogen bonds (HB) are very similar to those observed experimentally. Its low-energy side can be attributed to transitions between the EE ground state and a single localized excited level, in a picture that is different from that for the liquid solvent, where this portion has been associated with hydrogen-like s → p excitations. The blue tail, on the other hand, relates to transitions between the EE ground state and delocalized excited states, which is in line with the bound-to-continuum transition interpretations for the EE in liquid water. Finally, we find that, depending on the number of dangling HBs participating in the EE trap, its charge density may spontaneously break the spin degeneracy through exchange interactions with the surrounding electrons, displaying the many-electron quantum nature of the EE problem in ice Ih.

Switching a normal insulator into a topological insulator via electric field with application to phosphorene.

The study of topological insulators has generally involved search of materials that have this property as an innate quality, distinct from normal insulators. Here we focus on the possibility of converting a normal insulator into a topological one by application of an external electric field that shifts different bands by different energies and induces a specific band inversion, which leads to a topological state. Phosphorene is a two-dimensional (2D) material that can be isolated through mechanical exfoliation from layered black phosphorus, but unlike graphene and silicene, single-layer phosphorene has a large band gap (1.5-2.2 eV). Thus, it was unsuspected to exhibit band inversion and the ensuing topological insulator behavior. Using first-principles calculations with applied perpendicular electric field F⊥ on few-layer phosphorene we predict a continuous transition from the normal insulator to a topological insulator and eventually to a metal as a function of F⊥. The tuning of topological behavior with electric field would lead to spin-separated, gapless edge states, that is, quantum spin Hall effect. This finding opens the possibility of converting normal insulating materials into topological ones via electric field and making a multifunctional "field effect topological transistor" that could manipulate simultaneously both spin and charge carrier. We use our results to formulate some design principles for looking for other 2D materials that could have such an electrical-induced topological transition.

Tuning the thermoelectric properties of a single-molecule junction by mechanical stretching.

We theoretically investigate, as a function of the stretching, the behaviour of the thermoelectric properties - the Seebeck coefficient (S), the electronic heat conductance (κel) and the figure of merit (ZT) - of a molecule-based junction composed of a benzene-1,4-dithiolate molecule (BDT) coupled to Au(111) surfaces at room temperature. We show that the thermoelectric properties of a single molecule junction can be tuned by mechanic stretching. The Seebeck coefficient is positive, indicating that it is dominated by the HOMO. Furthermore, it increases as the HOMO level, which is associated to the sulphur atom, tends towards energies close to the Fermi energy. By modelling the transmission coefficient of the system as a single Lorentzian peak, we propose a scheme to obtain the maximum ZT of any molecular junction.

Size- effect induced high thermoelectric figure of merit in PbSe and PbTe nanowires.

The fundamental properties that compose the thermoelectric figure of merit are investigated in the confined systems of PbSe and PbTe nanowires, with the goal to improve the thermoelectric efficiency. Using the Landauer electronic transport theory, we verify that the figure of merit can be several times larger than the bulk value for nanowires with diameters down to the one nanometer scale. This enhancement in the thermoelectric efficiency is primarily due to the reduction of the thermal conductivity and an increase in the power factor. The origin of these desireable properties, that enable the transformation of heat into electricity, comes from the confinement effect which increases the density of states around the Fermi level, either for an n- or p-type system.

High-throughput inverse design and Bayesian optimization of functionalities: spin splitting in two-dimensional compounds.

The development of spintronic devices demands the existence of materials with some kind of spin splitting (SS). In this Data Descriptor, we build a database of ab initio calculated SS in 2D materials. More than that, we propose a workflow for materials design integrating an inverse design approach and a Bayesian inference optimization. We use the prediction of SS prototypes for spintronic applications as an illustrative example of the proposed workflow. The prediction process starts with the establishment of the design principles (the physical mechanism behind the target properties), that are used as filters for materials screening, and followed by density functional theory (DFT) calculations. Applying this process to the C2DB database, we identify and classify 358 2D materials according to SS type at the valence and/or conduction bands. The Bayesian optimization captures trends that are used for the rationalized design of 2D materials with the ideal conditions of band gap and SS for potential spintronics applications. Our workflow can be applied to any other material property.

How lignin sticks to cellulose-insights from atomic force microscopy enhanced by machine-learning analysis and molecular dynamics simulations.

Elucidating cellulose-lignin interactions at the molecular and nanometric scales is an important research topic with impacts on several pathways of biomass valorization. Here, the interaction forces between a cellulosic substrate and lignin are investigated. Atomic force microscopy with lignin-coated tips is employed to probe the site-specific adhesion to a cellulose film in liquid water. Over seven thousand force-curves are analyzed by a machine-learning approach to cluster the experimental data into types of cellulose-tip interactions. The molecular mechanisms for distinct types of cellulose-lignin interactions are revealed by molecular dynamics simulations of lignin globules interacting with different cellulose Iß crystal facets. This unique combination of experimental force-curves, data-driven analysis, and molecular simulations opens a new approach of investigation and updates the understanding of cellulose-lignin interactions at the nanoscale.