Functional Theory Band Structure Calculations Research Articles

Fe Site Order and Magnetic Properties of Fe1/4NbS2.

Transition-metal dichalcogenides (TMDs) have long been attractive to researchers for their diverse properties and high degree of tunability. Most recently, interest in magnetically intercalated TMDs has resurged due to their potential applications in spintronic devices. While certain compositions featuring the absence of inversion symmetry such as Fe1/3NbS2 and Cr1/3NbS2 have garnered the most attention, the diverse compositional space afforded through the host matrix composition as well as intercalant identity and concentration is large and remains relatively underexplored. Here, we report the magnetic ground state of Fe1/4NbS2 that was determined from low-temperature neutron powder diffraction as an A-type antiferromagnet. Despite the presence of overall inversion symmetry, the pristine compound manifests spin polarization induced by the antiferromagnetic order at generic k points, based on density functional theory band-structure calculations. Furthermore, by combining synchrotron diffraction, pair distribution function, and magnetic susceptibility measurements, we find that the magnetic properties of Fe1/4NbS2 are sensitive to the Fe site order, which can be tuned via electrochemical lithiation and thermal history.

Formation and Polymorphism of Semiconducting K2SiH6 and Strategy for Metallization.

K2SiH6, crystallizing in the cubic K2PtCl6 structure type (Fm3̅m), features unusual hypervalent SiH62- complexes. Here, the formation of K2SiH6 at high pressures is revisited by in situ synchrotron diffraction experiments, considering KSiH3 as a precursor. At the investigated pressures, 8 and 13 GPa, K2SiH6 adopts the trigonal (NH4)2SiF6 structure type (P3̅m1) upon formation. The trigonal polymorph is stable up to 725 °C at 13 GPa. At room temperature, the transition into an ambient pressure recoverable cubic form occurs below 6.7 GPa. Theory suggests the existence of an additional, hexagonal, variant in the pressure interval 3-5 GPa. According to density functional theory band structure calculations, K2SiH6 is a semiconductor with a band gap around 2 eV. Nonbonding H-dominated states are situated below and Si-H anti-bonding states are located above the Fermi level. Enthalpically feasible and dynamically stable metallic variants of K2SiH6 may be obtained when substituting Si partially by Al or P, thus inducing p- and n-type metallicity, respectively. Yet, electron-phonon coupling appears weak, and calculated superconducting transition temperatures are <1 K.

Bulk and surface electronic structure of NiBi3

We present a high-resolution, angle-resolved photoemission spectroscopy study of the normal electronic state of the superconducting ${\mathrm{NiBi}}_{3}$. Our experimental results show a complex Fermi surface structure with many sheets along the $\mathrm{\ensuremath{\Gamma}}\text{\ensuremath{-}}X$ and $\mathrm{\ensuremath{\Gamma}}\text{\ensuremath{-}}Y$ directions of the Brillouin zone. The band structure presents a topological surface state (TSS) at the high symmetry $\mathrm{\ensuremath{\Gamma}}$ point with a surface Dirac point at the energy $\ensuremath{-}0.185$ eV. The Dirac-like cone presents a linear dispersion along ${\mathrm{k}}_{x}$ while it presents saddle-like states along ${\mathrm{k}}_{y}$ located in the vicinity of the surface Dirac point. Our results are in good agreement with results of density functional theory band structure calculations. We also discuss the topological band structure of the ${\mathrm{NiBi}}_{3}$ compound.

Fermi surface of a system with strong valence fluctuations: Evidence for a noninteger count of valence electrons in EuIr2Si2

We present de Haas-van Alphen (dHvA) measurements on an Eu-based valence-fluctuating system. ${\mathrm{EuIr}}_{2}{\mathrm{Si}}_{2}$ exhibits a temperature-dependent, noninteger europium valence with ${\mathrm{Eu}}^{2.8+}$ at low temperatures. The comparison of experimental results from our magnetic-torque experiments in fields up to 32 T and density functional theory band-structure calculations with localized $4f$ electrons shows that the best agreement is reached for a Fermi surface based on a valence of ${\mathrm{Eu}}^{2.8+}$. The calculated quantum-oscillation frequencies for ${\mathrm{Eu}}^{3+}$ instead cannot explain all the experimentally observed frequencies. The effective masses, derived from the temperature dependence of the dHvA oscillation amplitudes, show not only a significant enhancement with masses up to $11\phantom{\rule{3.33333pt}{0ex}}{m}_{e}$ (${m}_{e}$ being the free electron mass), but also a magnetic-field dependence of the heaviest mass. We attribute the formation of these heavy masses to strong correlation effects resulting from valence fluctuations of $4f$ electrons being strongly hybridized with conduction electrons. The increase of the heavy masses with magnetic field likely results from the onset of the expected field-induced valence crossover that enhances these valence fluctuations but does not alter the Fermi-surface topology in the field range studied.

Ultrathin epitaxial Bi film growth on 2D HfTe2 template

Among ultrathin monoelemental two-dimensional (2D) materials, bismuthene, the single layer of heavier group-VΑ element bismuth (Bi), has been predicted to have large non trivial gap. Here, we demonstrate the growth of Bi films by molecular beam epitaxy on 2D-HfTe2 template. At the initial stage of Bi deposition (1–2 bilayers, BL), both the pseudocubic Bi(110) and the hexagonal Bi(111) phases are formed. When reaching 3 BL Bi, a transformation to pure hexagonal Bi(111) occurs. The electronic band structure of 3 BL Bi(111) films was measured by angle-resolved photoemission spectroscopy showing very good matching with the density functional theory band structure calculations of 3 BL free standing Bi(111). The grown Bi(111) thin film was capped with a protective Al2O3 layer and its stability under ambient conditions, necessary for practical applications and device fabrication, was confirmed by x-ray photoelectron spectroscopy and Raman spectroscopy.

Electronic structure of the metallic oxide ReO3

ReO${}_{3}$ is a remarkable transition metal oxide in that it has the highest conductivity of all oxides, comparable even with that of silver. Using state of the art bulk-sensitive angle-resolved photoelectron spectroscopy, the authors are able to observe clear dispersions of the Re 5$d$ and O 2$p$ derived bands as well as the momentum splitting of the Fermi surface due to the Re 5$d$ spin-orbit interaction. The experimental results are compared quantitatively to density functional theory band structure calculations, thereby providing a deeper understanding of the material class of the 5$d$ oxides.

Syntheses, Structures, and Physical Properties of Neutral Gold Dithiolate Complex, [Au(etdt)2]·THF

In order to develop new types of single-component molecular conductors with novel electronic structures and physical properties, the neutral gold dithiolate complex with an etdt (= ethylenedithiotetrathiafulvalenedithiolate) ligand, [Au(etdt)2] was prepared. However, unlike the reported single-component molecular metals, the neutral gold complex [Au(etdt)2]·THF (2) contains a solvent molecule of tetrahydrofuran (THF). The crystals of 2 form a two-dimensional conducting layer structure, which are separated by the terminal ethylene groups and THF molecules. The fairly high room-temperature conductivity of 0.2 S/cm and semiconducting behavior with a low activation energy of 0.1 eV of 2, is consistent with the result of the density functional theory band structure calculations. The observed non-magnetic behavior of 2 is caused from the dimeric structure of [Au(etdt)2] molecules.

The first silver bismuth borate, AgBi2B5O11.

The first silver bismuth borate, AgBi2B5O11 (silver dibismuth pentaborate), has been prepared via glass crystallization in the Ag2O-Bi2O3-B2O3 system and characterized by single-crystal X-ray diffraction. Its structure is derived from that of centrosymmetric Bi3B5O12 by ordered substitution of one Bi3+ ion for Ag+, which results in the disappearance of the mirror plane and inversion centre. Second harmonic generation (SHG) measurements confirm the acentric crystal structure. It is formed by [Bi2B5O11]∞ layers stretched along c and comprised of vertex-sharing B5O10 and BiO3 groups which incorporate the Ag+ cations. The new compound was characterized by thermal analysis, high-temperature powder X-ray diffraction, and vibrational and UV-Vis-NIR (near infrared) spectroscopy. Its thermal expansion is strongly anisotropic due to the presence of rigid B5O10 groups aligned in a parallel manner. The minimal value is observed along their axis [parallel to c, αc= 3.1 (1) × 10-6 K-1], while maximal values are observed in the ab plane [αa = 20.4 (2) and αb = 7.8 (2) × 10-6 K-1]. Upon heating, AgBi2B5O11 starts to decay above 684 K due to partial reduction of silver; incongruent melting is observed at 861 K. According to density functional theory (DFT) band-structure calculations, the new compound is a semiconductor with an indirect energy gap of 3.57 eV, which agrees with the experimental data (absorption onset at 380 nm).

Freestanding Borophene and Its Hybrids.

Borophene, an elemental metallic Dirac material is predicted to have unprecedented mechanical and electronic character. Need of substrate and ultrahigh vacuum conditions for deposition of borophene restricts its large-scale applications and significantly hampers the advancement of research on borophene. Herein, a facile and large-scale synthesis of freestanding atomic sheets of borophene through a novel liquid-phase exfoliation and the reduction of borophene oxide is demonstrated. Electron microscopy confirms the presence of β12 , X3 , and their intermediate phases of borophene; X-ray photoelectron spectroscopy, and scanning tunneling microscopy, corroborated with density functional theory band structure calculations, validate the phase purity and the metallic nature. Borophene with excellent anchoring capabilities is used for sensing of light, gas, molecules, and strain. Hybrids of borophene as well as that of reduced borophene oxide with other 2D materials are synthesized, and the predicted superior performance in energy storage is explored. The specific capacity of borophene oxide is observed to be ≈4941 mAh g-1 , which significantly exceeds that of existing 2D materials and their hybrids. These freestanding borophene materials and their hybrids will create a huge breakthrough in the field of 2D materials and could help to develop future generations of devices and emerging applications.

Benzoquinone-Bridged Heterocyclic Zwitterions as Building Blocks for Molecular Semiconductors and Metals.

In pursuit of closed-shell building blocks for single-component organic semiconductors and metals, we have prepared benzoquino-bis-1,2,3-thiaselenazole QS, a heterocyclic selenium-based zwitterion with a small gap (λmax = 729 nm) between its highest occupied and lowest unoccupied molecular orbitals. In the solid state, QS exists in two crystalline phases and one nanocrystalline phase. The structures of the crystalline phases (space groups R3 c and P21/ c) have been determined by high-resolution powder X-ray diffraction methods at ambient and elevated pressures (0-15 GPa), and their crystal packing patterns have been compared with that of the related all-sulfur zwitterion benzoquino-bis-1,2,3-dithiazole QT (space group Cmc21). Structural differences between the S- and Se-based materials are interpreted in terms of local intermolecular S/Se···N'/O' secondary bonding interactions, the strength of which varies with the nature of the chalcogen (S vs Se). While the perfectly two-dimensional "brick-wall" packing pattern associated with the Cmc21 phase of QT is not found for QS, all three phases of QS are nonetheless small band gap semiconductors, with σRT ranging from 10-5 S cm-1 for the P21/ c phase to 10-3 S cm-1 for the R3 c phase. The bandwidths of the valence and conduction bands increase with applied pressure, leading to an increase in conductivity and a decrease in thermal activation energy Eact. For the R3 c phase, band gap closure to yield an organic molecular metal with a σRT of ∼102 S cm-1 occurs at 6 GPa. Band gaps estimated from density functional theory band structure calculations on the ambient- and high-pressure crystal structures of QT and QS correlate well with those obtained experimentally.

An implementation of spin-orbit coupling for band structure calculations with Gaussian basis sets: Two-dimensional topological crystals of Sb and Bi.

We present an implementation of spin–orbit coupling (SOC) for density functional theory band structure calculations that makes use of Gaussian basis sets. It is based on the explicit evaluation of SOC matrix elements, both the radial and angular parts. For all-electron basis sets, where the full nodal structure is present in the basis elements, the results are in good agreement with well-established implementations such as VASP. For more practical pseudopotential basis sets, which lack nodal structure, an ad-hoc increase of the effective nuclear potential helps to capture all relevant band structure variations induced by SOC. In this work, the non-relativistic or scalar-relativistic Kohn–Sham Hamiltonian is obtained from the CRYSTAL code and the SOC term is added a posteriori. As an example, we apply this method to the Bi(111) monolayer, a paradigmatic 2D topological insulator, and to mono- and multilayer Sb(111) (also known as antimonene), the former being a trivial semiconductor and the latter a topological semimetal featuring topologically protected surface states.

Electronic Transport Properties of Carbon-Nanotube Networks: The Effect of Nitrate Doping on Intratube and Intertube Conductances

The conductivity of carbon nanotube (CNT) networks can be improved markedly by doping with nitric acid. In the present work, CNTs and junctions of CNTs functionalized with NO$_3$ molecules are investigated to understand the microscopic mechanism of nitric acid doping. According to our density functional theory band structure calculations, there is charge transfer from the CNT to adsorbed molecules indicating p-type doping. The average doping efficiency of the NO$_3$ molecules is higher if the NO$_3$ molecules form complexes with water molecules. In addition to electron transport along individual CNTs, we have also studied electron transport between different types (metallic, semiconducting) of CNTs. Reflecting the differences in the electronic structures of semiconducting and metallic CNTs, we have found that besides turning semiconducting CNTs metallic, doping further increases electron transport most efficiently along semiconducting CNTs as well as through a junction between them.

Optical investigation of the strong spin-orbit-coupled magnetic semimetal YbMnBi2

Strong spin-orbit coupling (SOC) can result in ground states with non-trivial topological properties. The situation is even richer in magnetic systems where the magnetic ordering can potentially have strong influence over the electronic band structure. The class of AMnBi$_2$ (A = Sr, Ca) compounds are important in this context as they are known to host massive Dirac fermions with strongly anisotropic dispersion that is believed to be due to the interplay between strong SOC and magnetic degrees of freedom. We report the optical conductivity of YbMnBi$_2$, a newly discovered member of this family and a proposed Weyl semi-metal (WSM) candidate with broken time reversal symmetry. Together with density functional theory (DFT) band structure calculations, we show how the complete conductivity can be interpreted as the sum of a intra-band Drude response and inter-band transitions. We argue that the canting of the magnetic moments that has been proposed to be essential for the realization of the WSM in an otherwise antiferromagnetically ordered system is not necessary to explain the optical conductivity. We believe our data is explained qualitatively by the uncanted magnetic structure with a small offset of the chemical potential from strict stochiometry. There is no definite evidence of bulk Weyl nodes, instead we see signatures of a gapped Dirac dispersion, common in other members of AMnBi$_2$ family or compounds with similar 2D network of Bi atoms.

Operation and Design of van der Waals Tunnel Transistors: A 3-D Quantum Transport Study

We propose a model Hamiltonian for van der Waals tunnel transistors (vdW-TFETs) relying on few physical parameters calibrated against density functional theory (DFT) band structure calculations. Based on this model, we develop a fully 3-D nonequilibrium Green’s function simulator including electron-phonon scattering, and we investigate some fundamental aspects and design challenges related to vdW-TFETs based on single-layer MoS2 and WTe2. In particular, we devote a specific analysis to the impact of top gate alignment and back-oxide thickness on the device performance. Our results suggest that the vdW-TFETs can provide very small values of subthreshold swing (SS) and fairly good ON-state current. However, these devices also pose specific design challenges related to the geometrical features of gated regions, and their ultimate SS may be lower limited by inelastic phonon scattering.

Density Functional Theory Modeling of Low-Loss Electron Energy-Loss Spectroscopy in Wurtzite III-Nitride Ternary Alloys.

In the present work, the dielectric response of III-nitride semiconductors is studied using density functional theory (DFT) band structure calculations. The aim of this study is to improve our understanding of the features in the low-loss electron energy-loss spectra of ternary alloys, but the results are also relevant to optical and UV spectroscopy results. In addition, the dependence of the most remarkable features with composition is tested, i.e. applying Vegard's law to band gap and plasmon energy. For this purpose, three wurtzite ternary alloys, from the combination of binaries AlN, GaN, and InN, were simulated through a wide compositional range (i.e., Al x Ga1-x N, In x Al1-x N, and In x Ga1-x N, with x=[0,1]). For this DFT calculations, the standard tools found in Wien2k software were used. In order to improve the band structure description of these semiconductor compounds, the modified Becke-Johnson exchange-correlation potential was also used. Results from these calculations are presented, including band structure, density of states, and complex dielectric function for the whole compositional range. Larger, closer to experimental values, band gap energies are predicted using the novel potential, when compared with standard generalized gradient approximation. Moreover, a detailed analysis of the collective excitation features in the dielectric response reveals their compositional dependence, which sometimes departs from a linear behavior (bowing). Finally, an advantageous method for measuring the plasmon energy dependence from these calculations is explained.

The mechanism of charge density wave in Pt-based layered superconductors: SrPt2As2 and LaPt2Si2.

The intriguing coexistence of the charge density wave (CDW) and superconductivity in SrPt2As2 and LaPt2Si2 has been investigated based on the ab initio density functional theory band structure and phonon calculations. We have found that the CDW instabilities for both cases arise from the q-dependent electron-phonon coupling with quasi-nesting feature of the Fermi surface. The band structure obtained by the band-unfolding technique reveals the sizable q-dependent electron-phonon coupling responsible for the CDW instability. The local split distortions of Pt atoms in the [As-Pt-As] layers play an essential role in driving the five-fold supercell CDW instability as well as the phonon softening instability in SrPt2As2. By contrast, the CDW and phonon softening instabilities in LaPt2Si2 occur without split distortions of Pt atoms. The phonon calculations suggest that the CDW and the superconductivity coexist in [X-Pt-X] layers (X = As or Si) for both cases.

Compton Profile Study and Electron Momentum Density Reconstruction in Hexagonal Mg

Four directional Compton profiles (CPs) of a hexagonal magnesium single crystal have been measured with high momentum resolution (0.12 a.u.) using 115.6 keV synchrotron radiation in SPring-8. Experimental CP anisotropies were compared with augmented plane waves (APW), Korringa–Kohn–Rostocker (KKR), and the latest density functional theory (DFT) band structure calculations. In order to reconstruct the full three-dimensional valence electron momentum density distribution, maximum entropy method (MEM) was applied. 3D electron momentum densities obtained using MEM were compared (after appropriate integration) with 2D electron momentum density reconstructed using Cormack's method. MEM has proved its advantage as a technique for reconstructing density distributions when initial information is insufficient and noisy. The 3D valence electron momentum density of hexagonal Mg was successfully reconstructed using as few as four experimental or five theoretical Compton profiles. As is shown, despite a clear anisotrop...

Van der Waals bonding and the quasiparticle band structure of SnO from first principles

In this work we have investigated the structural and electronic properties of SnO, which is built up from layers kept together by van der Waals (vdW) forces. The combination of a vdW functional within density functional theory (DFT) and quasiparticle band structure calculations within the $GW$ approximation provides accurate values for the lattice parameters, atomic positions, and the electronic band structure including the fundamental (indirect) and the optical (direct) band gap without the need of experimental or empirical input. A systematic comparison is made between different levels of self-consistency within the $GW$ approach ${$following the scheme of Shishkin et al. [Phys. Rev. B 75, 235102 (2007)]$}$ and the results are compared with DFT and hybrid functional results. Furthermore, the effect of the vdW-corrected functional as a starting point for the $GW$ calculation of the band gap has been investigated. Finally, we studied the effect of the vdW functional on the electron charge density.

Bandgap tuning of mono- and bilayer graphene doped with group IV elements

We report density functional theory band structure calculations of graphene doped with group IV elements. A bandgap as high as 2.13 eV is calculated for a single layer of graphene doped with Si while Ge and Sn doping reduce this bandgap for equal doping concentrations. Bilayers of doped graphene are also studied and it is found that the bandgap of these materials is less than that of the single layer counterparts. Finally, a transverse electric field is applied to the doped bilayers and it is found that the bandgap is inversely proportional to the electric field strength in contrast to what has been observed in the case of pristine bilayers. Carrier effective masses were calculated and in general the effective masses of electrons and holes are found to be similar.

Role ofp-dands-dinteractions in the electronic structure and band gap of Zn1−xMxO (M=Cr, Mn, Fe, Co, Ni, and Cu): Photoelectron and optical spectroscopy and first-principles band structure calculations

We report an investigation on the effect of $p$-$d$ and $s$-$d$ interactions in the electronic structure, and especially in the band-gap value, of wurtzite wide-gap diluted magnetic semiconductors Zn${}_{1\ensuremath{-}x}$${M}_{x}$O ($M=\mathrm{Cr}$, Mn, Fe, Co, Ni, Cu). Thin films prepared by pulsed laser deposition are investigated by means of optical absorption at low-temperature and photoelectron spectroscopy. Pure wurzite phase is shown to be maintained for Co and Mn concentrations up to 25$%$ and for Cr up to 10$%$, while in the case of Fe, Ni, and Cu, other phases are present for concentrations higher than 5, 2, and 1$%$, respectively. The band gap of the Zn${}_{1\ensuremath{-}x}$${M}_{x}$O alloy increases at a rate of 9, 22, 4, and 23 meV/$%$$M$ for $M=\mathrm{Cr}$, Mn, Fe, and Co, respectively, and decreases at a rate of about $\ensuremath{-}$14 and $\ensuremath{-}$10 meV/$%$$M$ for $M=\mathrm{Ni}$ and Cu. Photoelectron spectroscopy of the Zn${}_{1\ensuremath{-}x}$${M}_{x}$O valence band for $M=\mathrm{Mn}$ and Co shows that the emergence of the transition metal-related photoemission peak is clearly correlated to a larger binding energy of the O 2$p$ valence-band peaks. A simple model of $p$-$d$ and $s$-$d$ interaction is proposed in which the decrease of Zn 3$d$ electron density below the valence band and the increase of $M$ 3$d$ electron density for $M=\mathrm{Cr}$ to Co lead to higher binding energies of the valence-band maximum and, thus, to a larger band gap. In contrast, for Ni and Cu the 3$d$ electrons lie below the valence-band maximum and push it to lower binding energies, thus decreasing the band gap. This simple model is basically confirmed by first-principles density functional theory band structure calculations. Detailed analyses of the band structures and densities of states show that the $p$-$d$ interaction leads to an increase of the band gap for $M=\mathrm{Mn}$ to Co but a decrease for $M=\mathrm{Ni}$ and Cu. They also suggest that the $s$-$d$ interaction plays the major role or contributes as much as the $p$-$d$ interaction in leading to the increase of the band gap for $M=\mathrm{Cr}$ and Mn, respectively.