Mechanochemical Synthesis of Non-Solvated Dialkylalumanyl Anion and XPS Characterization of Al(I) and Al(II) Species.

A non-solvated alkyl-substituted Al(I) anion dimer was synthesized by a reduction of haloalumane precursor using a mechanochemical method. The crystallographic and theoretical analysis revealed its structure and electronic properties. Experimental XPS analysis of the Al(I) anions with reference compounds revealed the lower Al 2p binding energy corresponds to the lower oxidation state of Al species. It should be emphasized that the experimentally obtained XPS binding energies were reproduced by delta SCF calculations and were linearly correlated with NPA charges and 2p orbital energies.

Electronic band structure change with structural transition of buckled Au2X monolayers induced by strain.

This study investigates the strain-induced structural transitions of η ↔ θ and the changes in electronic band structures of Au2X (X = S, Se, Te, Si, Ge) and Au4SSe. We focus on Au2S monolayers, which can form multiple meta-stable monolayers theoretically, including η-Au2S, a buckled penta-monolayer composed of a square Au lattice and S adatoms. The θ-Au2S is regarded as a distorted structure of η-Au2S. Based on density functional theory (DFT) calculations using a generalized gradient approximation, the conduction and the valence bands of θ-Au2S intersect at the Γ point, leading to linear dispersion, whereas η-Au2S has a band gap of 1.02 eV. The conduction band minimum depends on the specific Au-Au bond distance, while the valence band maximum depends on both Au-S and Au-Au interactions. The band gap undergoes significant changes during the η ↔ θ phase transition of Au2S induced by applying tensile or compressive in-plane biaxial strain to the lattice. Moreover, substituting S atoms with other elements alters the electronic band structures, resulting in a variety of physical properties without disrupting the fundamental Au lattice network. Therefore, the family of Au2X monolayers holds potential as materials for atomic scale network devices.

Metallic State of a Mixed-Sequence Oligomer Salt That Models Doped PEDOT Family.

Modern organic conductors are typically low-molecular-weight or polymer-based materials. Low-molecular-weight materials can be characterized using crystallographic information, allowing structure-conductivity relationships to be established and conduction mechanisms to be understood. However, controlling their conductive properties through molecular structural modulation is often challenging because of their relatively narrow conjugate areas. In contrast, polymer-based materials have highly π-conjugated structures with wide molecular-weight distributions, and their structural inhomogeneity makes characterizing their structures difficult. Thus, we focused on the less-explored intermediate, i.e., single-molecular-weight oligomers that model doped poly(3,4-ethylenedioxythiophene) (PEDOT). The dimer and trimer models provided clear structures; however, the short oligomers led to much lower conductivities (<10-3 S cm-1) than that of doped PEDOT. Herein, we elongated the oligomer to a tetramer through geometrical tuning based on a mixed sequence. The "P-S-S-P" sequence (S: 3,4-ethylenedithiothiophene; P: 3,4-(2',2'-dimethypropylenedioxy)thiophene) with twisted S-S enhanced the solubility and chemical stability. The subsequent oxidation process planarized the oligomer and expanded the conjugate area. Interestingly, the sequence involving sterically bulky outer P units allowed the doped oligomer to form a pitched π-stack in the single-crystal form. This enabled the inclusion of excess counter anions, which modulated the band filling. The combined effects of conjugate area expansion and band-filling modulation significantly increased the room-temperature conductivity to 36 S cm-1. This is the highest value reported for a single-crystalline oligomer conductor. Furthermore, a metallic state was observed above room temperature in a single-crystalline oligoEDOT for the first time. This unique mixed-sequence strategy for oligomer-based conductors enabled the precise control of conductive properties.

Ambipolar Nickel Dithiolene Complex Semiconductors: From One- to Two-Dimensional Electronic Structures Based upon Alkoxy Chain Lengths.

Air-stable single-component ambipolar organic semiconductors that conduct both holes and electrons are highly desired but have been rarely realized. Neutral nickel bis(dithiolene) complexes are promising candidates that fulfill the stringent electronic requirements of shallow HOMO levels and deep LUMO levels, which can reduce the carrier injection barrier to overcome the work function of gold electrodes and ensure air stability. However, most nickel bis(dithiolene) analogs that have been characterized as ambipolar semiconductors have twisted molecular structures that hinder the effective intermolecular interactions required for carrier conduction. To address this issue, we synthesized planar alkoxy-substituted nickel bis(dithiolene) analogs that facilitate dense packing with effective intermolecular interactions. Remarkably, changing the methoxy substituents to ethoxy or propoxy groups led to a dramatic change in the packing mode, from one-dimensional to herringbone-like, while maintaining effective intermolecular interactions. These materials overcome the usual trade-off between crystallinity and solubility; they are highly crystalline, even in their film forms, and are highly soluble in organic solvents. They are therefore readily solution-processable to form semiconducting layers with well-defined and well-ordered structures in field-effect transistors. Devices based on these compounds exhibited efficient ambipolar characteristics, even after several months of exposure to air, achieving high carrier mobilities of up to 10-2 cm2 V-1 s-1 and large on/off ratios of up to 105, which are the top-class performances achieved for a single-component ambipolar semiconductor material driven in air.

Hydrogen-induced Sulfur Vacancies on the MoS2 Basal Plane Studied by Ambient Pressure XPS and DFT Calculations.

Sulfur vacancy on an MoS2 basal plane plays a crucial role in device performance and catalytic activity; thus, an understanding of the electronic states of sulfur vacancies is still an important issue. We investigate the electronic states on an MoS2 basal plane by ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and density functional theory calculations while heating the system in hydrogen. The AP-XPS results show a decrease in the intensity ratio of S 2p to Mo 3d, indicating that sulfur vacancies are formed. Furthermore, low-energy components are observed in Mo 3d and S 2p spectra. To understand the changes in the electronic states induced by sulfur vacancy formation at the atomic scale, we calculate the core-level binding energies for the model vacancy surfaces. The calculated shifts for Mo 3d and S 2p with the formation of sulfur vacancy are consistent with the experimentally observed binding energy shifts. Mulliken charge analysis indicates that this is caused by an increase in the electronic density associated with the Mo and S atoms around the sulfur vacancy as compared to the pristine surface. The present investigation provides a guideline for sulfur vacancy engineering.

Elucidation of the atomic-scale processes of dissociative adsorption and spillover of hydrogen on the single atom alloy catalyst Pd/Cu(111).

Hydrogen spillover is a crucial process in the selective hydrogenation reactions on Pd/Cu single atom alloy catalysts. In this study, we report the atomic-scale perspective of these processes on the single atom alloy catalyst Pd/Cu(111) based on the experimental and theoretical results, including infrared reflection absorption spectroscopy (IRAS), temperature programmed desorption (TPD), high-resolution X-ray photoelectron spectroscopy (HR-XPS), and density functional theory (DFT) calculations for core-level excitation. The hydrogen spillover onto Cu(111) was successfully observed in real time using time-resolved IRAS measurements at 80 K. The chemical shifts of Pd 3d5/2 indicate that H2 is dissociated and adsorbed at the Pd site. In addition, a "two-step" chemical shift of the Pd 3d5/2 binding energy was observed, indicating two types of hydrogen adsorption states at the Pd site. The proposed mechanism of the hydrogen dissociation and spillover processes is as follows: (i) a hydrogen molecule is dissociated at a Pd site, and the hydrogen atoms are adsorbed on the Pd site; (ii) the number of hydrogen atoms on the Pd site increases up to three; and (iii) the hydrogen atoms will spill over onto the Cu surface.

The Simplest Model for Doped Poly(3,4-ethylenedioxythiophene) (PEDOT): Single-crystalline EDOT Dimer Radical Cation Salts.

Although doped poly(3,4-ethylenedioxythiophene) (PEDOT) is extensively used in electronic devices, their molecular-weight distributions and inadequately defined structures have hindered the elucidation of their underlying conduction mechanism. In this study, we introduce the simplest discrete oligomer models: EDOT dimer radical cation salts. Single-crystal structural analyses revealed their one-dimensional (1D) columnar structures, in which the donors were uniformly stacked. Band calculations identified 1D metallic band structures with a strong intracolumnar orbital interaction (band width W≈1 eV), implying the origin of the high conductivity of doped PEDOT. Interestingly, the salts exhibited semiconducting behavior reminiscent of genuine Mott states as a result of electron-electron repulsion (U) dominant over W. This study realized basic models with tunable W and U to understand the conduction mechanism of doped PEDOT through structural modification in oligomers, including the conjugation length.

The Simplest Model for Doped Poly(3,4-ethylenedioxythiophene) (PEDOT): Single-crystalline EDOT Dimer Radical Cation Salts.

Invited for the cover of this issue is the group of Tomoko Fujino and Hatsumi Mori at the University of Tokyo. The image depicts the structural information of doped PEDOT uncovered by the single-crystalline EDOT dimer model. Read the full text of the article at .10.1002/chem.202005333.

Formation of BN-covered silicene on ZrB2/Si(111) by adsorption of NO and thermal processes.

We have investigated the adsorption and thermal reaction processes of NO with silicene spontaneously formed on the ZrB2/Si(111) substrate using synchrotron radiation x-ray photoelectron spectroscopy (XPS) and density-functional theory calculations. NO is dissociatively adsorbed on the silicene surface at 300 K. An atomic nitrogen is bonded to three Si atoms most probably by a substitutional adsorption with a Si atom of silicene (N≡Si3). An atomic oxygen is inserted between two Si atoms of the silicene (Si-O-Si). With increasing NO exposure, the two-dimensional honeycomb silicene structure gets destroyed, judging from the decay of typical Si 2p spectra for silicene. After a large amount of NO exposure, the oxidation state of Si becomes Si4+ predominantly, and the intensity of the XPS peaks of the ZrB2 substrate decreases, indicating that complicated silicon oxinitride species have developed three-dimensionally. By heating above 900 K, the oxide species start to desorb from the surface, but nitrogen-bonded species still exist. After flashing at 1053 K, no oxygen species is observed on the surface; SiN species are temporally formed as a metastable species and BN species also start to develop. In addition, the silicene structure is restored on the ZrB2/Si(111) substrate. After prolonged heating at 1053 K, most of nitrogen atoms are bonded to B atoms to form a BN layer at the topmost surface. Thus, BN-covered silicene is formed on the ZrB2/Si(111) substrate by the adsorption of NO at 300 K and prolonged heating at 1053 K.

Li deposition and desolvation with electron transfer at a silicon/propylene-carbonate interface: transition-state and free-energy profiles by large-scale first-principles molecular dynamics.

We report the result of a large-scale first-principles molecular dynamics simulation under different electric biases performed to understand the charge transfer process coupling with lithium deposition and desolvation processes. We applied the effective screening medium (ESM) method to control the bias across the electrode/solution interface, and simulated a series of Li de-solvation and Li-deposition reactions occurring under the bias. Solvated Li+ in the bulk propylene carbonate migrates to the Si electrode surface and gradually de-solvates through the transition state. Introducing the blue-moon ensemble method, we determined the possible structures and activation energies for the transition states.

Absolute Binding Energies of Core Levels in Solids from First Principles.

A general method is presented to calculate absolute binding energies of core levels in metals and insulators, based on a penalty functional and an exact Coulomb cutoff method in the framework of density functional theory. The spurious interaction of core holes between supercells is avoided by the exact Coulomb cutoff method, while the variational penalty functional enables us to treat multiple splittings due to chemical shift, spin-orbit coupling, and exchange interaction on equal footing, both of which are not accessible by previous methods. It is demonstrated that the absolute binding energies of core levels for both metals and insulators are calculated by the proposed method in a mean absolute (relative) error of 0.4 eV (0.16%) for eight cases compared to experimental values measured with x-ray photoemission spectroscopy within a generalized gradient approximation to the exchange-correlation functional.

A method of orbital analysis for large-scale first-principles simulations.

An efficient method of calculating the natural bond orbitals (NBOs) based on a truncation of the entire density matrix of a whole system is presented for large-scale density functional theory calculations. The method recovers an orbital picture for O(N) electronic structure methods which directly evaluate the density matrix without using Kohn-Sham orbitals, thus enabling quantitative analysis of chemical reactions in large-scale systems in the language of localized Lewis-type chemical bonds. With the density matrix calculated by either an exact diagonalization or O(N) method, the computational cost is O(1) for the calculation of NBOs associated with a local region where a chemical reaction takes place. As an illustration of the method, we demonstrate how an electronic structure in a local region of interest can be analyzed by NBOs in a large-scale first-principles molecular dynamics simulation for a liquid electrolyte bulk model (propylene carbonate + LiBF4).

Experimental evidence for epitaxial silicene on diboride thin films.

As the Si counterpart of graphene, silicene may be defined as an at least partially sp2-hybridized, atom-thick honeycomb layer of Si that possesses π-electronic bands. Here we show that two-dimensional, epitaxial silicene forms through surface segregation on zirconium diboride thin films grown on Si wafers. A particular buckling of silicene induced by the epitaxial relationship with the diboride surface leads to a direct π-electronic band gap at the Γ point. These results demonstrate that the buckling and thus the electronic properties of silicene are modified by epitaxial strain.

Large-scale first-principles molecular dynamics for electrochemical systems with O(N) methods.

A method for large-scale first-principles molecular dynamics (MD) simulations on electrochemical systems has been developed by combining the effective screening medium (ESM) method with O(N) density functional theory (DFT). This implementation has been significantly simplified by the introduction of neutral atom potentials, which minimizes the modifications to existing DFT code. In order to demonstrate ability of this implementation, it has been applied to an electrochemical system consisting of a H-Si(111) electrode, which is a candidate anode for high-capacity Li-ion secondary batteries, and a propylene carbonate (PC) solvent to simulate how PC molecules in the vicinity of the electrode surface respond to an imposed electric field. The large-scale MD simulation clearly demonstrates that the combination of the ESM and O(N) DFT methods provides a useful tool for first-principles investigation of complicated electrochemical systems such as high-capacity batteries.

Effect of Method of Removing Caries-Affected Dentin on the Bond Strength of Composite Resin to Root Canal Dentin.

The adhesion of composite resin to caries-affected dentin differs from the adhesion of resin to sound dentin. We evaluated the bond strengths of dual-cure resin composites applied to caries-affected root canal dentin under various clinical conditions and using several caries removal indicators. In the dye stain 1 group, caries were removed to a pale pink stain level using a caries detector. In the dye stain 2 group, caries were removed to a stain-free level using a caries detector. In the probing group, caries were removed to the level of hardness based on probing with a sharp explorer. Additionally, a sound dentin group was used as a control. We compared the resin composite microtensile bond strengths and failure mode distribution among the groups. The bond strengths (MPa) of the probing (64.6 ± 11.9) and the sound dentin (68.7 ± 11.1) groups were significantly higher than those of the dye stain 1 (46.9 ± 7.9) and 2 (47.5 ± 8.4) groups (p < 0.05). The removal of caries-affected dentin using a dentin-hardness-based technique showed higher tensile strength than that using a dye stain technique involving removal to any color level. Thus, the caries removal technique used on root canal dentin affects the bond strength of the resin composite.

Densest ternary sphere packings.

We present our exhaustive exploration of the densest ternary sphere packings (DTSPs) for 45 radius ratios and 237 kinds of compositions, which is a packing problem of three kinds of hard spheres with different radii, under periodic boundary conditions by a random structure searching method. To efficiently explore DTSPs we further develop the searching method based on the piling-up and iterative balance methods [Koshoji et al., Phys. Rev. E 103, 023307 (2021)2470-004510.1103/PhysRevE.103.023307]. The unbiased exploration identifies diverse 38 putative DTSPs appearing on phase diagrams in which 37 DTSPs of them are discovered in the study. The structural trend of DTSPs changes depending especially on the radius of small spheres. In case that the radius of small spheres is relatively small, structures of many DTSPs can be understood as derivatives of densest binary sphere packings (DBSPs), while characteristic structures specific to the ternary system emerge as the radius of small spheres becomes larger. In addition to DTSPs, we reveal a lot of semi-DTSPs (SDTSPs) which are obtained by excluding DBSPs in the calculation of phase diagram, and investigate the correspondence of DTSPs and SDTSPs with real crystals based on the space group, showing a considerable correspondence of SDTSPs having high symmetries with real crystals including Cu_{2}GaSr and ThCr_{2}Si_{2} structures. Our study suggests that the diverse structures of DBSPs, DTSPs, and SDTSPs can be effectively used as structural prototypes for searching complex crystal structures.

Diverse densest binary sphere packings and phase diagram.

We revisit the densest binary sphere packings (DBSPs) under periodic boundary conditions and present an updated phase diagram, including newly found 12 putative densest structures over the x-α plane, where x is the relative concentration and α is the radius ratio of the small and large spheres. To efficiently explore the DBSPs, we develop an unbiased random search approach based on both the piling-up method to generate initial structures in an unbiased way and the iterative balance method to optimize the volume of a unit cell while keeping the overlap of hard spheres minimized. With those two methods, we have discovered 12 putative DBSPs and thereby the phase diagram is updated, while our results are consistent with those of a previous study [Hopkins et al., Phys. Rev. E 85, 021130 (2012)]PLEEE81539-375510.1103/PhysRevE.85.021130 with a small correction for the case of 12 or fewer spheres in the unit cell. Five of the discovered 12 DBSPs are identified in the small radius range of 0.42≤α≤0.50, where several structures are competitive to each other with respect to packing fraction. Through the exhaustive search, diverse dense packings are discovered and, accordingly, we find that packing structures achieve high packing fractions by introducing distortion and/or combining a few local dense structural units. Furthermore, we investigate the correspondence of the DBSPs with crystals based on the space group. The result shows that many structural units in real crystals, e.g., LaH_{10} and SrGe_{2-δ} being high-pressure phases, can be understood as DBSPs. The correspondence implies that the densest sphere packings can be used effectively as structural prototypes for searching complex crystal structures, especially for high-pressure phases.

Structural investigation of ternary PdRuM (M = Pt, Rh, or Ir) nanoparticles using first-principles calculations.

We perform first-principles calculations and Monte Carlo sampling to investigate the structures of ternary PdRuM (M = Pt, Rh, or Ir) nanoparticles (NPs) with respect to three different spherical shapes. The morphologies include hexagonal close-packed (hcp), truncated-octahedral (fcc), and icosahedral (Ih, fcc) shapes with 57, 55, and 55 atoms, respectively. The calculations show that the atomic position is dominant in determining the stability of the ternary NPs. For bare ternary NPs, Pd and Ru atoms favor a location on the vertex sites and the core, respectively, which can be understood by the surface energy of the corresponding slab models. For single-crystalline NPs, the binary shell could be either a solid solution or a segregation alloy depending on composition and morphology. However, polycrystalline Ih NPs only form segregated binary shells surrounding the Ru core. Such configurations tend to minimize the surface lattice to gain more energy from the d orbital of the transition metals. In addition to the bare NPs, we study the oxidized ternary NPs. The results show that the Ru atoms penetrate outwards from the core to the surface reducing the oxidation formation energy. Furthermore, oxygen adsorption facilitates Pt, Pd, and Pd penetration into the PdRuPt, PdRuRh, and PdRuIr NPs, respectively. Most of the oxide shells are a solid solution, except for the PdRuRh NP with an Ih shape, which is found to be in a segregation shell. The free energy calculation reveals that the pure hcp NPs are thermodynamically unstable under oxygen-rich conditions. This work clearly demonstrates the structural trends of small ternary NPs and their oxidation, unveiling that the structural trends can be understood by the surface formation energy and the interplay between adsorbent and adsorbing oxygen atoms.

Numerical evaluation of electron repulsion integrals for pseudoatomic orbitals and their derivatives.

A numerical method to calculate the four-center electron-repulsion integrals for strictly localized pseudoatomic orbital basis sets has been developed. Compared to the conventional Gaussian expansion method, this method has an advantage in the ease of combination with O(N) density functional calculations. Additional mathematical derivations are also presented including the analytic derivatives of the integrals with respect to atomic positions and spatial damping of the Coulomb interaction due to the screening effect. In the numerical test for a simple molecule, the convergence up to 10(-5) hartree in energy is successfully obtained with a feasible cost of computation.

OpenMX Viewer: A web-based crystalline and molecular graphical user interface program.

The OpenMX Viewer (Open source package for Material eXplorer Viewer) is a web-based graphical user interface (GUI) program for visualization and analysis of crystalline and molecular structures and 3D grid data in the Gaussian cube format such as electron density and molecular orbitals. The web-based GUI program enables us to quickly visualize crystalline and molecular structures by dragging and dropping XYZ, CIF, or OpenMX input/output files, and analyze static/dynamic structural properties conveniently in a web browser. Several basic functionalities such as analysis of Mulliken charges, molecular dynamics, geometry optimization and band structure are included. In addition, based on marching cubes, marching tetrahedra and surface nets algorithms with Affine transformation, 3D isosurface techniques are supported to visualize electron density and molecular/crystalline orbitals in the cube format with superposition of a crystalline or molecular structure. Furthermore, the Band Structure Viewer is implemented for showing a band structure in a web browser. By accessing the website of the OpenMX Viewer, the latest OpenMX Viewer is always available for users to visualize various structures and analyze their properties without installations, upgrades, updates, registration, sign-in and terminal commands.