Showing papers on "Electronic structure published in 2016"

Scalable Quantum Simulation of Molecular Energies

Abstract: We report the first electronic structure calculation performed on a quantum computer without exponentially costly precompilation. We use a programmable array of superconducting qubits to compute the energy surface of molecular hydrogen using two distinct quantum algorithms. First, we experimentally execute the unitary coupled cluster method using the variational quantum eigensolver. Our efficient implementation predicts the correct dissociation energy to within chemical accuracy of the numerically exact result. Second, we experimentally demonstrate the canonical quantum algorithm for chemistry, which consists of Trotterization and quantum phase estimation. We compare the experimental performance of these approaches to show clear evidence that the variational quantum eigensolver is robust to certain errors. This error tolerance inspires hope that variational quantum simulations of classically intractable molecules may be viable in the near future.

A new understanding of the photocatalytic mechanism of the direct Z-scheme g-C3N4/TiO2 heterostructure

Abstract: Constructing a TiO2 based heterostructure is a very effective strategy for enhancing photocatalytic performance. The details of the electronic structure, interfacial interaction, and photogenerated carrier separation are important for explaining the photocatalytic properties of a heterostructure. Herein, the density of states, charge distribution, and the band offset of the monolayer g-C3N4/TiO2 heterojunction are systematically investigated through the hybrid DFT method. Results indicated that the valence band offset and the conduction band offset of the g-C3N4/TiO2 heterostructure were 0.40 and 0.18 eV, respectively. Interfacial interaction made the TiO2 surface with negative charge, whereas the g-C3N4 surface with positive charge, which led to the formation of a built-in electric field at the interface. Under illumination, the built-in electric field accelerates the transfer of photoexcited electrons in the CB of TiO2 into the VB of g-C3N4, thus resulting in the photoexcited electrons and holes naturally accumulating in the CB of g-C3N4 and the VB of TiO2, respectively. The photoexcited electrons and holes gathering in different surface regions efficiently prolonged the lifetime of photogenerated carriers. Meanwhile, electrons in the CB of g-C3N4 and holes in the VB of TiO2 had a stronger redox ability. Therefore, g-C3N4/TiO2 is a direct Z-scheme photocatalyst, and the Z-scheme heterostructure mechanism can well explain the improved photocatalytic activity of the g-C3N4/TiO2 heterostructure.

MN15-L: A New Local Exchange-Correlation Functional for Kohn–Sham Density Functional Theory with Broad Accuracy for Atoms, Molecules, and Solids

Abstract: Kohn–Sham density functional theory is widely used for applications of electronic structure theory in chemistry, materials science, and condensed-matter physics, but the accuracy depends on the quality of the exchange-correlation functional. Here, we present a new local exchange-correlation functional called MN15-L that predicts accurate results for a broad range of molecular and solid-state properties including main-group bond energies, transition metal bond energies, reaction barrier heights, noncovalent interactions, atomic excitation energies, ionization potentials, electron affinities, total atomic energies, hydrocarbon thermochemistry, and lattice constants of solids. The MN15-L functional has the same mathematical form as a previous meta-nonseparable gradient approximation exchange-correlation functional, MN12-L, but it is improved because we optimized it against a larger database, designated 2015A, and included smoothness restraints; the optimization has a much better representation of transition ...

What is moving in hybrid halide perovskite solar cells

Abstract: Organic-inorganic semiconductors, which adopt the perovskite crystal structure, have perturbed the landscape of contemporary photovoltaics research. In this Account, we discuss the internal motion of methylammonium lead iodide (CH$_3$NH$_3$PbI$_3$) and formamidinium lead iodide ([CH(NH$_2$)$_2$]PbI$_3$), covering: (i) molecular rotation-libration in the cuboctahedral cavity; (ii) drift and diffusion of large electron and hole polarons; (iii) transport of charged ionic defects. These processes give rise to a range of properties that are unconventional for photovoltaic materials, including frequency-dependent permittivity, low electron-hole recombination rates, and current-voltage hysteresis. Multi-scale simulations - drawing from electronic structure, ab initio molecular dynamic and Monte Carlo techniques - have been combined with neutron scattering and ultra-fast vibrational spectroscopy to qualify the nature and timescales of the motions. Recent experimental evidence and theoretical models for simultaneous electron transport and ion transport in these materials has been presented, suggesting they are mixed-mode conductors with similarities to metal oxide perovskites developed for battery and fuel cell applications. We expound on the implications of these effects for the photovoltaic action. The temporal behaviour found in hybrid perovskites introduces a sensitivity in materials characterisation to the time and length scale of the measurement, as well as the history of each sample. It also poses significant challenges for accurate materials and device simulations. Herein, we critically discuss the atomistic origin of the dynamic processes.

Modeling Polymorphic Molecular Crystals with Electronic Structure Theory

Abstract: Interest in molecular crystals has grown thanks to their relevance to pharmaceuticals, organic semiconductor materials, foods, and many other applications. Electronic structure methods have become an increasingly important tool for modeling molecular crystals and polymorphism. This article reviews electronic structure techniques used to model molecular crystals, including periodic density functional theory, periodic second-order Moller-Plesset perturbation theory, fragment-based electronic structure methods, and diffusion Monte Carlo. It also discusses the use of these models for predicting a variety of crystal properties that are relevant to the study of polymorphism, including lattice energies, structures, crystal structure prediction, polymorphism, phase diagrams, vibrational spectroscopies, and nuclear magnetic resonance spectroscopy. Finally, tools for analyzing crystal structures and intermolecular interactions are briefly discussed.

Highly efficient and tuneable spin-to-charge conversion through Rashba coupling at oxide interfaces

Abstract: The spin-orbit interaction couples the electrons' motion to their spin. Accordingly, passing a current in a material with strong spin-orbit coupling generates a transverse spin current (spin Hall effect, SHE) and vice-versa (inverse spin Hall effect, ISHE). The emergence of SHE and ISHE as charge-to-spin interconversion mechanisms offers a variety of novel spintronics functionalities and devices, some of which do not require any ferromagnetic material. However, the interconversion efficiency of SHE and ISHE (spin Hall angle) is a bulk property that rarely exceeds ten percent, and does not take advantage of interfacial and low-dimensional effects otherwise ubiquitous in spintronics hetero- and mesostructures. Here, we make use of an interface-driven spin-orbit coupling mechanism - the Rashba effect - in the oxide two-dimensional electron system (2DES) LaAlO3/SrTiO3 to achieve spin-to-charge conversion with unprecedented efficiency. Through spin-pumping, we inject a spin current from a NiFe film into the oxide 2DES and detect the resulting charge current, which can be strongly modulated by a gate voltage. We discuss the amplitude of the effect and its gate dependence on the basis of the electronic structure of the 2DES.

Large anomalous Hall effect in a half-Heusler antiferromagnet

Abstract: The anomalous Hall effect is usually associated with ferromagnets but a large anomalous Hall response can be found in topologically non-trivial half-Heusler antiferromagnets thanks to Berry phase effects associated with symmetry breaking. The quantum mechanical (Berry) phase of the electronic wavefunction plays a critical role in the anomalous1,2 and spin Hall effects3,4, including their quantized limits5,6,7. While progress has been made in understanding these effects in ferromagnets8, less is known in antiferromagnetic systems. Here we present a study of antiferromagnet GdPtBi, whose electronic structure is similar to that of the topologically non-trivial HgTe (refs 9,10,11), and where the Gd ions offer the possibility to tune the Berry phase via control of the spin texture. We show that this system supports an anomalous Hall angle ΘAH > 0.1, comparable to the largest observed in bulk ferromagnets12 and significantly larger than in other antiferromagnets13. Neutron scattering measurements and electronic structure calculations suggest that this effect originates from avoided crossing or Weyl points that develop near the Fermi level due to a breaking of combined time-reversal and lattice symmetries. Berry phase effects associated with such symmetry breaking have recently been explored in kagome networks14,15,16,17; our results extend this to half-Heusler systems with non-trivial band topology. The magnetic textures indicated here may also provide pathways towards realizing the topological insulating and semimetallic states9,10,11,18,19 predicted in this material class.

Perspective: Kohn-Sham density functional theory descending a staircase

Abstract: This article presents a perspective on Kohn-Sham density functional theory (KS-DFT) for electronic structure calculations in chemical physics. This theory is in widespread use for applications to both molecules and solids. We pay special attention to several aspects where there are both concerns and progress toward solutions. These include: 1. The treatment of open-shell and inherently multiconfigurational systems (the latter are often called multireference systems and are variously classified as having strong correlation, near-degeneracy correlation, or high static correlation; KS-DFT must treat these systems with broken-symmetry determinants). 2. The treatment of noncovalent interactions. 3. The choice between developing new functionals by parametrization, by theoretical constraints, or by a combination. 4. The ingredients of the exchange-correlation functionals used by KS-DFT, including spin densities, the magnitudes of their gradients, spin-specific kinetic energy densities, nonlocal exchange (Hartree-Fock exchange), nonlocal correlation, and subshell-dependent corrections (DFT+U). 5. The quest for a universal functional, where we summarize some of the success of the latest Minnesota functionals, namely MN15-L and MN15, which were obtained by optimization against diverse databases. 6. Time-dependent density functional theory, which is an extension of DFT to treat time-dependent problems and excited states. The review is a snapshot of a rapidly moving field, and—like Marcel Duchamp—we hope to convey progress in a stimulating way.

The electronic structure of iridium oxide electrodes active in water splitting.

Abstract: Iridium oxide based electrodes are among the most promising candidates for electrocatalyzing the oxygen evolution reaction, making it imperative to understand their chemical/electronic structure. However, the complexity of iridium oxide's electronic structure makes it particularly difficult to experimentally determine the chemical state of the active surface species. To achieve an accurate understanding of the electronic structure of iridium oxide surfaces, we have combined synchrotron-based X-ray photoemission and absorption spectroscopies with ab initio calculations. Our investigation reveals a pre-edge feature in the O K-edge of highly catalytically active X-ray amorphous iridium oxides that we have identified as O 2p hole states forming in conjunction with IrIII. These electronic defects in the near-surface region of the anionic and cationic framework are likely critical for the enhanced activity of amorphous iridium oxides relative to their crystalline counterparts.

Electronic Processes within Quantum Dot-Molecule Complexes.

Abstract: The subject of this review is the colloidal quantum dot (QD) and specifically the interaction of the QD with proximate molecules. It covers various functions of these molecules, including (i) ligands for the QDs, coupled electronically or vibrationally to localized surface states or to the delocalized states of the QD core, (ii) energy or electron donors or acceptors for the QDs, and (iii) structural components of QD assemblies that dictate QD–QD or QD–molecule interactions. Research on interactions of ligands with colloidal QDs has revealed that ligands determine not only the excited state dynamics of the QD but also, in some cases, its ground state electronic structure. Specifically, the article discusses (i) measurement of the electronic structure of colloidal QDs and the influence of their surface chemistry, in particular, dipolar ligands and exciton-delocalizing ligands, on their electronic energies; (ii) the role of molecules in interfacial electron and energy transfer processes involving QDs, inclu...

Charge transport and localization in atomically coherent quantum dot solids.

Abstract: Epitaxial attachment of quantum dots into ordered superlattices enables the synthesis of quasi-two-dimensional materials that theoretically exhibit features such as Dirac cones and topological states, and have major potential for unprecedented optoelectronic devices. Initial studies found that disorder in these structures causes localization of electrons within a few lattice constants, and highlight the critical need for precise structural characterization and systematic assessment of the effects of disorder on transport. Here we fabricated superlattices with the quantum dots registered to within a single atomic bond length (limited by the polydispersity of the quantum dot building blocks), but missing a fraction (20%) of the epitaxial connections. Calculations of the electronic structure including the measured disorder account for the electron localization inferred from transport measurements. The calculations also show that improvement of the epitaxial connections will lead to completely delocalized electrons and may enable the observation of the remarkable properties predicted for these materials.

Cu-In Halide Perovskite solar absorbers

Abstract: The long-term chemical instability and the presence of toxic Pb in otherwise stellar solar absorber APbX$_{3}$ have hindered their large-scale commercialization. Previously explored ways to achieve Pb-free halide perovskites involved replacing Pb$^{2+}$ with other similar M$^{2+}$ cations in ns$^2$ electron configuration, e.g., Sn$^{2+}$ or by Bi$^{3+}$ (plus Ag$^+$), but unfortunately this showed either poor stability (M = Sn) or weakly absorbing oversized indirect gaps (M = Bi), prompting concerns that perhaps stability and good optoelectronic properties might be contraindicated. Herein, we exploit the electronic structure underpinning of classic Cu[In,Ga]Se$_{2}$ (CIGS) chalcopyrite solar absorbers to design Pb-free halide perovskites by transmuting 2Pb to the pair [B$^{IB}$ + C$^{III}$]. The resulting group of double perovskites with formula A$_2$BCX$_6$ (A = K, Rb, Cs; B = Cu, Ag; C = Ga, In; X = Cl, Br, I) benefits from the ionic, yet narrow-gap character of halide perovskites, and at the same time borrows the advantage of the strong and rapidly rising Cu(d)/Se(p) $\rightarrow$ Ga/In(s/p) valence-to-conduction-band absorption spectra known from CIGS. This constitutes a new group of CuIn-based Halide Perovskite (CIHP). Our first-principles calculations guided by such design principles indicate that the CIHPs class has members with clear thermodynamic stability, showing rather strong direct-gap optical transitions, and manifesting a wide-range of tunable gap values (from zero to about 2.5 eV) and combination of light electron and heavy-light hole effective masses. Materials screening of candidate CHIPs then identifies the best-of-class Rb$_2$[CuIn]Cl$_6$, Rb$_2$[AgIn]Br$_6$ and Cs$_2$[AgIn]Br$_6$, having direct band gaps of 1.36, 1.46 and 1.50 eV, and a theoretical spectroscopic limited maximal efficiency comparable to chalcopyrites and CH$_3$NH$_3$PbI$_3$.

Giant edge state splitting at atomically precise graphene zigzag edges

Abstract: Zigzag edges of graphene nanostructures host localized electronic states that are predicted to be spin-polarized. However, these edge states are highly susceptible to edge roughness and interaction with a supporting substrate, complicating the study of their intrinsic electronic and magnetic structure. Here, we focus on atomically precise graphene nanoribbons whose two short zigzag edges host exactly one localized electron each. Using the tip of a scanning tunnelling microscope, the graphene nanoribbons are transferred from the metallic growth substrate onto insulating islands of NaCl in order to decouple their electronic structure from the metal. The absence of charge transfer and hybridization with the substrate is confirmed by scanning tunnelling spectroscopy, which reveals a pair of occupied/unoccupied edge states. Their large energy splitting of 1.9 eV is in accordance with ab initio many-body perturbation theory calculations and reflects the dominant role of electron–electron interactions in these localized states.

Quantum hydrogen-bond symmetrization in the superconducting hydrogen sulfide system

Abstract: The quantum nature of the proton can crucially affect the structural and physical properties of hydrogen compounds. For example, in the high-pressure phases of H2O, quantum proton fluctuations lead to symmetrization of the hydrogen bond and reduce the boundary between asymmetric and symmetric structures in the phase diagram by 30 gigapascals (ref. 3). Here we show that an analogous quantum symmetrization occurs in the recently discovered sulfur hydride superconductor with a superconducting transition temperature Tc of 203 kelvin at 155 gigapascals--the highest Tc reported for any superconductor so far. Superconductivity occurs via the formation of a compound with chemical formula H3S (sulfur trihydride) with sulfur atoms arranged on a body-centred cubic lattice. If the hydrogen atoms are treated as classical particles, then for pressures greater than about 175 gigapascals they are predicted to sit exactly halfway between two sulfur atoms in a structure with Im3m symmetry. At lower pressures, the hydrogen atoms move to an off-centre position, forming a short H-S covalent bond and a longer H···S hydrogen bond in a structure with R3m symmetry. X-ray diffraction experiments confirm the H3S stoichiometry and the sulfur lattice sites, but were unable to discriminate between the two phases. Ab initio density-functional-theory calculations show that quantum nuclear motion lowers the symmetrization pressure by 72 gigapascals for H3S and by 60 gigapascals for D3S. Consequently, we predict that the Im3m phase dominates the pressure range within which the high Tc was measured. The observed pressure dependence of Tc is accurately reproduced in our calculations for the phase, but not for the R3m phase. Therefore, the quantum nature of the proton fundamentally changes the superconducting phase diagram of H3S.

Spin-orbit excitation energies, anisotropic exchange, and magnetic phases of honeycomb RuCl3

Abstract: Using quantum chemistry calculations we shed fresh light on the electronic structure and magnetic properties of RuCl3, a proposed realization of the honeycomb Kitaev spin model. It is found that the nearest-neighbor Kitaev exchange K is weaker than in 5d5 Ir oxides but still larger than other effective spin couplings. The electronic-structure computations also indicate a ferromagnetic K in the halide, which is supported by a detailed analysis of the field-dependent magnetization. From exact-diagonalization calculations for extended Kitaev-Heisenberg Hamiltonians we additionally find that a transition from zigzag order to a spin-liquid ground state can be induced in RuCl3 with external magnetic field.

Imaging electrostatically confined Dirac fermions in graphene quantum dots

Abstract: Relativistic Dirac fermions can be locally confined in nanoscale graphene quantum dots using electrostatic gating, and directly imaged using scanning tunnelling microscopy before escaping via Klein tunnelling. Electrostatic confinement of charge carriers in graphene is governed by Klein tunnelling, a relativistic quantum process in which particle–hole transmutation leads to unusual anisotropic transmission at p–n junction boundaries1,2,3,4,5. Reflection and transmission at these boundaries affect the quantum interference of electronic waves, enabling the formation of novel quasi-bound states6,7,8,9,10,11,12. Here we report the use of scanning tunnelling microscopy to map the electronic structure of Dirac fermions confined in quantum dots defined by circular graphene p–n junctions. The quantum dots were fabricated using a technique involving local manipulation of defect charge within the insulating substrate beneath a graphene monolayer13. Inside such graphene quantum dots we observe resonances due to quasi-bound states and directly visualize the quantum interference patterns arising from these states. Outside the quantum dots Dirac fermions exhibit Friedel oscillation-like behaviour. Bolstered by a theoretical model describing relativistic particles in a harmonic oscillator potential, our findings yield insights into the spatial behaviour of electrostatically confined Dirac fermions.

Dependence of elastic and optical properties on surface terminated groups in two-dimensional MXene monolayers: a first-principles study

Abstract: Density functional theory is used to investigate the elastic and optical properties as well as the crystal and electronic structures of two-dimensional Ti2CT2 and Ti3C2T2 (T = F, O, and OH) MXene monolayers. It is found that the elastic stiffness, optical response, crystal structure and the electronic structure show strong dependence on the surface terminated groups often formed with MXene during the etching process. The elastic stiffness maintains only with the surface termination of O atoms, but a large degradation is present in the surface terminations of F and OH atoms. The low adsorption and reflectivity in the range from infrared to ultraviolet rays account for the high transmittance of Ti3C2T2 that has been experimentally observed, and it is predicted that Ti2CT2 will have higher optical transmittance in this range. The calculations also demonstrate the presence of the optical bandgap in Ti2CO2, which renders its potential applications in optical and electronic devices.

Electronic structure theory of weakly interacting bilayers

Abstract: We derive electronic structure models for weakly interacting bilayers such as graphene-graphene and graphene--hexagonal boron nitride, based on density functional theory calculations followed by Wannier transformation of electronic states. These transferable interlayer coupling models can be applied to investigate the physics of bilayers with arbitrary translations and twists. The functional form, in addition to the dependence on the distance, includes the angular dependence that results from higher angular momentum components in the Wannier ${p}_{z}$ orbitals. We demonstrate the capabilities of the method by applying it to a rotated graphene bilayer, which produces the analytically predicted renormalization of the Fermi velocity, Van Hove singularities in the density of states, and moir\'e pattern of the electronic localization at small twist angles. We further extend the theory to obtain the effective couplings by integrating out neighboring layers. This approach is instrumental for the design of van der Walls heterostructures with desirable electronic features and transport properties and for the derivation of low-energy theories for graphene stacks, including proximity effects from other layers.

Observation of large topologically trivial Fermi arcs in the candidate type-II Weyl semimetal WT e 2

Abstract: The authors present here several advances towards a comprehensive understanding of WTe${}_{2}$. Using microfocus laser ARPES, they resolve for the first time the distinct electronic structure of both inequivalent top and bottom (001) surfaces of WTe${}_{2}$. Moreover, they demonstrate for the first time the presence of large surface state Fermi arcs on both surfaces. Using surface electronic structure calculations, they further demonstrate that these Fermi arcs are topologically trivial and that their existence is independent of the presence of type-II Weyl points in the bulk band structure. Contrary to common belief, the observation of surface state Fermi arcs is thus not suitable to robustly identify a type-II Weyl semimetal. Finally, the authors use the observation of Fermi arcs and distinct top and bottom surfaces to clarify the controversial bulk electronic structure of WTe${}_{2}$. They show that the bulk Fermi surface is formed by three-dimensional electron and hole pockets with areas that are found to be in good agreement with transport experiments, with the exception of small hole pockets that have not been observed in quantum oscillation experiments.

A Direct Mechanism of Ultrafast Intramolecular Singlet Fission in Pentacene Dimers

Abstract: Interest in materials that undergo singlet fission (SF) has been catalyzed by the potential to exceed the Shockley–Queisser limit of solar power conversion efficiency. In conventional materials, the mechanism of SF is an intermolecular process (xSF), which is mediated by charge transfer (CT) states and depends sensitively on crystal packing or molecular collisions. In contrast, recently reported covalently coupled pentacenes yield ∼2 triplets per photon absorbed in individual molecules: the hallmark of intramolecular singlet fission (iSF). However, the mechanism of iSF is unclear. Here, using multireference electronic structure calculations and transient absorption spectroscopy, we establish that iSF can occur via a direct coupling mechanism that is independent of CT states. We show that a near-degeneracy in electronic state energies induced by vibronic coupling to intramolecular modes of the covalent dimer allows for strong mixing between the correlated triplet pair state and the local excitonic state, d...

Ab initio phonon coupling and optical response of hot electrons in plasmonic metals

Abstract: Ultrafast laser measurements probe the nonequilibrium dynamics of excited electrons in metals with increasing temporal resolution. Electronic structure calculations can provide a detailed microscopic understanding of hot electron dynamics, but a parameter-free description of pump-probe measurements has not yet been possible, despite intensive research, because of the phenomenological treatment of electron-phonon interactions. We present ab initio predictions of the electron-temperature dependent heat capacities and electron-phonon coupling coefficients of plasmonic metals. We find substantial differences from free-electron and semiempirical estimates, especially in noble metals above transient electron temperatures of 2000 K, because of the previously neglected strong dependence of electron-phonon matrix elements on electron energy. We also present first-principles calculations of the electron-temperature dependent dielectric response of hot electrons in plasmonic metals, including direct interband and phonon-assisted intraband transitions, facilitating complete theoretical predictions of the time-resolved optical probe signatures in ultrafast laser experiments.

A Semi‐Conductive Copper–Organic Framework with Two Types of Photocatalytic Activity

Abstract: Based on the newly designed ligand 4′-(3,5-dicarboxyphenyl)-4,2′:6′,4′′-terpyridine (DCTP), a unique semi-conductive 3D framework {[CuΙCuΙΙ2(DCTP)2]NO3⋅1.5 DMF}n (1) with a narrow band gap of 2.1 eV, was obtained and structurally characterized. DFT calculations with van de Waals correction employed to explore the electronic structure of 1, clearly revealed its semi-conductive behavior. Furthermore, we found that 1 exhibits a superior band alignment with water to produce hydrogen and degrade organic pollutants. Without adding any photosensitizers, 1 displays an efficiently photocatalytic hydrogen production in water based on the photo-generated electrons under UV/Vis light. 1 also exhibits excellent photo-degradation of methyl blue under visible-light owing to the strong oxidization of excited holes. It is the first example of MOFs with doubly photocatalytic activities related to photo-generated electrons and holes, respectively.

Direct band gaps in group IV-VI monolayer materials: Binary counterparts of phosphorene

Abstract: We perform systematic investigation on the geometric, energetic, and electronic properties of group IV-VI binary monolayers $(\mathit{XY})$, which are the counterparts of phosphorene, by employing density functional theory based electronic structure calculations. For this purpose, we choose the binary systems $XY$ consisting of equal numbers of group IV $(X$ = C, Si, Ge, Sn) and group VI elements ($Y$ = O, S, Se, Te) in three geometrical configurations, the puckered, buckled and planar structures. The results of binding energy calculations show that all the binary systems studied are energetically stable. It is observed that, the puckered structure, similar to that of phosphorene, is the energetically most stable geometric configuration. Moreover, the binding energies of buckled configuration are very close to those of the puckered configuration. Our results of electronic band structure predict that puckered SiO and CSe are direct band semiconductors with gaps of 1.449 and 0.905 eV, respectively. Band structure of CSe closely resembles that of phosphorene. Remaining group IV-VI binary monolayers in the puckered configuration and all the buckled monolayers are also semiconductors, but with indirect band gaps. Importantly, we find that the difference between indirect and direct band gaps is very small for many puckered monolayers. Thus there is a possibility of making these systems undergo transition from indirect to direct band gap semiconducting state by a suitable external influence. Indeed, we show in the present work that seven binary monolayers, namely, SnS, SiSe, GeSe, SnSe, SiTe, GeTe, and SnTe become direct band gap semiconductors when they are subjected to a small mechanical strain ($\ensuremath{\le}3%$). This makes nine out of sixteen binary monolayers studied in the present work direct band gap semiconductors. Thus there is a possibility of utilizing these binary counterparts of phosphorene in future light-emitting diodes and solar cells.

ExoMol line lists - XVIII. The high-temperature spectrum of VO

Abstract: An accurate line list, VOMYT, of spectroscopic transitions is presented for hot VO. The 13 lowest electronic states are considered. Curves and couplings are based on initial ab initio electronic structure calculations and then tuned using available experimental data. Dipole moment curves, used to obtain transition intensities, are computed using high levels of theory (e.g. MRCI/aug-cc-pVQZ using state-specific or minimal-state complete active space for dipole moments). This line list contains over 277 million transitions between almost 640 000 energy levels. It covers the wavelengths longer than 0.29 μm and includes all transitions from energy levels within the lowest nine electronic states which have energies less than 20 000 cm−1 to upper states within the lowest 13 electronic states which have energies below 50 000 cm−1. The line lists give significantly increased absorption at infrared wavelengths compared to currently available VO line lists. The full line lists is made available in electronic form via the CDS database and at www.exomol.com.

Impact of Film Stoichiometry on the Ionization Energy and Electronic Structure of CH3NH3PbI3 Perovskites

Abstract: The electronic structure of a large sample set of CH3 NH3 PbI3 -based perovskites is studied. Combined investigations by UV/X-ray photoelectron spectroscopy and X-ray diffraction reveal that interstitials present in the film lead to changes in the occupied density of states close to the valence band, which in turn influences the performance of solar cells. Changes in elemental composition tune the ionization energy of the perovskite film by almost 1 eV without introducing significant amounts of gap states.

Single-Crystal and Electronic Structure of a 1.3 nm Indium Phosphide Nanocluster.

Abstract: Magic-sized nanoclusters have been implicated as mechanistically relevant intermediates in the synthesis of group III-V quantum dots. Herein we report the single-crystal X-ray diffraction structure of a carboxylate-ligated indium phosphide magic-sized nanocluster at 0.83 A resolution. The structure of this cluster, In37P20(O2CR)51, deviates from that of known crystal phases and possesses a non-stoichiometric, charged core composed of a series of fused 6-membered rings. The cluster is completely passivated by bidentate carboxylate ligands exhibiting predominantly bridging binding modes. The absorption spectrum of the cluster shows an asymmetric line shape that is broader than what would be expected from a homogeneous sample. A combination of computational and experimental evidence suggests that the spectral line width is a result of multiple, discrete electronic transitions that couple to vibrations of the nanocrystal lattice. The product of reaction of this nanocluster with 1 equiv of water has also been ...

Equiatomic quaternary Heusler alloys: a material perspective for spintronic applications

Abstract: Half-metallic ferromagnetic (HMF) materials show high spin polarization and are therefore interesting to researchers due to their possible applications in spintronic devices. In these materials, while one spin sub band has a finite density of states at the Fermi level, the other sub band has a gap. Because of their high Curie temperature and tunable electronic structure, HMF Heusler alloys have a special importance among the HMF materials. Full Heusler alloys with the stoichiometric composition X2YZ (where X and Y are the transition metals and Z is a sp element) have the cubic structure with four interpenetrating fcc sublattices. When each of these four fcc sublattices is occupied by different atoms, a quaternary Heusler structure with different structural symmetry is obtained. Recently, these equiatomic quaternary Heusler alloys (EQHAs) with 1:1:1:1 stoichiometry have attracted a lot of attention due to their superior magnetic and transport properties.

Effect of metal cation replacement on the electronic structure of metalorganic halide perovskites: Replacement of lead with alkaline-earth metals

Abstract: Organic and inorganic lead halogen perovskites, and in particular, CH3NH3PbI3, have during the last years emerged as a class of highly efficient solar cell materials. Herein we introduce metalorganic halogen perovskite materials for energy-relevant applications based on alkaline-earth metals. Based on the classical notion of Goldschmidt's rules and quantum mechanical considerations, the three alkaline-earth metals, Ca, Sr, and Ba, are shown to be able to exchange lead in the perovskite structure. The three alkaline-earth perovskites, CH3NH3CaI3, CH3NH3SrI3, and CH3NH3BaI3, as well as the reference compound, CH3NH3PbI3, are in this paper investigated with density functional theory (DFT) calculations, which predict these compounds to exist as stable perovskite materials, and their electronic properties are explored. A detailed analysis of the projected molecular orbital density of states and electronic band structure from DFT calculations were used for interpretation of the band-gap variations in these materials and for estimation of the effective masses of the electrons and holes. Neglecting spin-orbit effects, the band gap of MACaI(3), MASrI(3), and MABaI(3) were estimated to be 2.95, 3.6, and 3.3 eV, respectively, showing the relative change expected for metal cation exchange. The shifts in the conduction band (CB) edges for the alkaline-earth perovskites were quantified using scalar relativistic DFT calculations and tight-binding analysis, and were compared to the situation in the more extensively studied lead halide perovskite, CH3NH3PbI3, where the change in the work function of the metal is the single most important factor in tuning the CB edge and band gap. The results show that alkaline-earth-based organometallic perovskites will not work as an efficient light absorber in photovoltaic applications but instead could be applicable as charge-selective contact materials. The rather high CB edge and the wide band gap together with the large difference of the electron and hole effective masses make them good candidates for n-type selective layers in hot carrier injection solar cell devices together with some light absorber candidates. The fact that they have similar lattice constants as the lead perovskite and suitable positions of the valence band edges open up the possibility to use them also as thin epitaxial p-type hole selective contacts in combination with the lead halogen perovskite materials. This can lead to both charge selectivity as well as to superior crystal growth of lead perovskite with less contact stress, which is interesting for further investigations.

X-ray and Electron Spectroscopy of Water

Abstract: Here we present an overview of recent developments of X-ray and electron spectroscopy to probe water at different temperatures. Photon-induced ionization followed by detection of electrons from either the O 1s level or the valence band is the basis of photoelectron spectroscopy. Excitation between the O 1s and the unoccupied states or occupied states is utilized in X-ray absorption and X-ray emission spectroscopies. These techniques probe the electronic structure of the liquid phase and show sensitivity to the local hydrogen-bonding structure. Both experimental aspects related to the measurements and theoretical simulations to assist in the interpretation are discussed in detail. Different model systems are presented such as the different bulk phases of ice and various adsorbed monolayer structures on metal surfaces.