Changes In Binding Energy Research Articles

Environmentally sensitive theory of electronic and optical transitions in atomically thin semiconductors

Due to their small size, atomically thin materials are expected to exhibit electronic properties that are highly sensitive to their environment. However, atomically thin semiconductors on a variety of substrates, as well as in their bulk layered phase, exhibit an absorption onset at roughly the same energy. The authors provide a semianalytic theory of the quasiparticle band gap in atomically thin semiconductors and show that environment-induced changes are almost exactly canceled by changes in the exciton binding energy, leaving the absorption onset nearly constant. The presented theory sets limits on the prospect of environmental engineering in atomically thin materials.

Comparison of external electric and magnetic fields effect on binding energy of hydrogenic donor impurity in different shaped quantum wells

The effects of external electric and magnetic fields on the ground state binding energy of hydrogenic donor impurity are compared in square, V-shaped, and parabolic quantum wells. With the effective-mass envelope-function approximation theory, the ground state binding energies of hydrogenic donor impurity in InGaAsP/InP QWs are calculated through the plane wave basis method. The results indicate that as the quantum well width increases, the binding energy changes most fast in SQW. When the well width is fixed, the binding energy is the largest in VQW for the donor impurity located near the center of QWs. For the smaller and larger well width, the electric field effect on binding energy is the most significant in VQW and SQW, respectively. The magnetic field effect on binding energy is the most significant in VQW. The combined effects of electric and magnetic fields on the binding energy of hydrogenic donor impurity are qualitative consistent in different shaped QWs.

Electrochemical, top-down nanostructured pseudocapacitive electrodes for enhanced specific capacitance and cycling efficiency.

Stabilization of the electroactive redox centers on ideally polarisable conductive electrodes is a critical challenge for realizing stable, high performing pseudocapacitive energy storage devices. Here, we report a top-down, electrochemical nanostructuring route based on voltammetric cycling to stabilize β-MnO2 on a single walled carbon nanotube (CNT) scaffold from a MnMoO4 precursor. Such in situ nanostructuring results in controlled disintegration of an ∼8 μm almond like structure to form ∼29 nm β-MnO2 resulting in a 59% increase in the specific surface area and a 31% increase in the porosity of the pseudocapacitive electrode. Consequently, the specific capacitance and areal capacitance increase by ∼75% and ∼40%, respectively. Such controlled, top-down nanostructuring is confirmed through binding energy changes to Mo 3d, C 1s, O 1s and Mn 2p respectively in XPS. Furthermore, Raman spectral mapping confirms the sequential nanostructuring initiating from the interface of CNTs with MnMoO4 and proceeding outwards. Thus, the process yields the final CNT/β-MnO2 electrode that is electrically conductive, facilitates rapid charge transfer, and has increased capacitance and longer stability. Furthermore, the charge-transfer resistance and equivalent resistance are significantly lower compared to conventional activated carbon based electrodes.

The Influence of Inert Ions on the Reactivity of Manganese Oxides

Inert ion doping is a possible method to modify electrical conductivity and catalytic activity of transition-metal oxide electrocatalysts. Despite the importance of dopants, little is known about the underlying mechanisms for the change of the system properties. We have performed density functional theory calculations to investigate the influence of different valent ions on the O2 evolution reaction activity of β-MnO2 and Mn2O3. While Mn2O3 is unaffected by dopants, β-MnO2 is strongly affected by ions placed in a subsurface position. Doping does not affect the ion charge at the active site, but instead it effects the bond character. This is concluded through an analysis of the density overlap regions indicator and the density of states showing that the partially covalent nature of the bonds in β-MnO2 is responsible for the changes in the adsorbate binding energies. This mechanism is not active in the mostly ionic Mn2O3. These results highlight the need to explicitly consider the detailed bonding situation and to go beyond simple charge transfer considerations when describing doping of transition metal oxide catalysts.

Electric field and impurity effect on nonlinear optical rectification of a double cone like quantum dot

In this work, we have investigated the effect of electric field and impurity position on nonlinear optical rectification of a double cone like quantum dot in the effective mass approximation and by using compact density-matrix formalism. We have calculated the energy levels and wave functions using finite element method (FEM) in the presence of impurity and influence of electric field. The results show that: (i) the binding energy changes with the impurity position and it is changed by the applied electric field, (ii) nonlinear optical rectification peak position of this system present the blue or red shift due to the applied electric field and changing the impurity position. (iii) for low electric field, impurity position plays an important role in electronic and optical properties, but for larger electric field, impurity position role becomes non-significant. (iv) the optical rectification changes due to the impurity position and the electric field are considerable.

Reversible Self-Assembly of Water-Soluble Gold(I) Complexes.

The reaction of the gold polymers containing bipyridyl and terpyridyl units, [Au(C≡CC15H10N3)]n and [Au(C≡CC10H7N2)]n, with the water-soluble phosphines 1,3,5-triaza-7-phosphatricyclo[3.3.1.13.7]decane and 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane gives rise to the formation of four gold(I) alkynyl complexes that self-assemble in water (H2O) and dimethyl sulfoxide (DMSO), through different intermolecular interactions, with an impact on the observed luminescence displayed by the supramolecular assemblies. A detailed analysis carried out by NMR studies performed in different DMSO/deuterated H2O mixtures indicates the presence of two different assembly modes in the aggregates: (i) chain assemblies, which are based mainly on aurophilic interactions, and (ii) stacked assemblies, which are based on Au···π and π···π interactions. These different supramolecular environments can also be detected by their intrinsic optical properties (differences in absorption and emission spectra) and are predicted by the changes in the relative binding energy from density functional theory calculations carried out in DMSO and H2O. Small-angle X-ray scattering (SAXS) experiments performed in the same mixture of solvents are in agreement with the formation of aggregates in all cases. The aromatic units chosen, bipyridine and terpyridine, allow the use of external stimuli to reversibly change the aggregation state of the supramolecular assemblies. Interaction with the Zn2+ cation is observed to disassemble the aggregates, while encapsulating agents competing for Zn2+ complexation revert the process to the aggregation stage, as verified by SAXS and NMR. The adaptive nature of the supramolecular assemblies to the metal-ion content is accompanied by significant changes in the absorption and emission spectra, signaling the aggregation state and also the content on Zn2+.

Bimetallic Co-Mn Perovskite Fluorides as Highly-Stable Electrode Materials for Supercapacitors.

Bimetallic Co-Mn perovskite fluorides (KCox Mn1-x F3 , denoted as K-Co-Mn-F) with various Co/Mn ratios (1:0, 12:1, 6:1, 3:1, 1:1, 1:3, 0:1) were prepared through a one-pot solvothermal strategy and further used as electrode materials for supercapacitors. The optimal K-Co-Mn-F candidate (Co/Mn=6:1) showed a size range of 0.1-1 μm and uniform elemental distribution; exhibiting small changes in XRD peaks and XPS binding energy in comparison to the bare K-Co-F and K-Mn-F, due to the structural/electronic effects. Owing to the stronger synergistic effect of Co/Mn redox species, the K-Co-Mn-F (Co/Mn=6:1) electrode exhibited superior specific capacity and rate behavior (113-100 C g-1 at 1-16 Ag-1 ) together with excellent cycling stability (118 % for 5000 cycles at 8 Ag-1 ), and the activated carbon (AC)//K-Co-Mn-F (Co/Mn=6:1) asymmetric capacitor showed superior energy and power densities (8.0-2.4 Wh kg-1 at 0.14-8.7 kW kg-1 ) along with high cycling stability (90 % for 10 000 cycles at 5 Ag-1 ).

Tautomerization of Thymine Using Ultraviolet Light.

Ultraviolet-light-induced changes to the nucleobase thymine deposited onto a MoS2 surface were studied using photoelectron spectroscopy and first-principles calculations. These measurements suggest changes in the molecular structure indicated by changes in core electron binding energies. The experimental work has been interpreted by means of ab initio calculations using coupled cluster singles and doubles (CCSD) linear response theory. Contrary to the expected behavior, i.e., the dimerization of two thymine molecules into a pyrimidine dimer, a shift between two tautomeric forms was observed upon UV-exposure. Exposure to ionizing radiation is known to induce damage in many biological molecules, and the present work gives additional insight into its effects on thymine, the interactions of the molecules, and finally how certain UV photoproducts may be avoided.

Crystal structure and thermodynamic dissection of chitin oligosaccharide binding to the LysM module of chitinase-A from Pteris ryukyuensis

We determined the crystal structure of a LysM module from Pteris ryukyuensis chitinase-A (PrLysM2) at a resolution of 1.8 Å. Structural and binding analysis of PrLysM2 indicated that this module recognizes chitin oligosaccharides in a shallow groove comprised of five sugar-binding subsites on one side of the molecule. The free energy changes (ΔGr°) for binding of (GlcNAc)6, (GlcNAc)5, and (GlcNAc)4 to PrLysM2 were determined to be −5.4, −5,4 and −4.6 kcal mol−1, respectively, by ITC. Thermodynamic dissection of the binding energetics of (GlcNAc)6 revealed that the driving force is the enthalpy change (ΔHr° = −11.7 ± 0.2 kcal/mol) and the solvation entropy change (−TΔSsolv° = −5.9 ± 0.6 kcal/mol). This is the first description of thermodynamic signatures of a chitin oligosaccharide binding to a LysM module.

Simultaneous effects of pressure and temperature on the optical transition energies in a Ga0.7In0.3N/GaN quantum ring

Simultaneous effects of pressure and temperature on electronic and optical properties are studied in a Ga0.7In0.3N/GaN quantum ring using variational formulism. The changes in exciton binding energy due to the applications of hydrostatic pressure and temperature are obtained taking into account the geometrical confinement. The transition energies of interband and intersubband as a function of hydrostatic pressure, at a constant temperature, are obtained. The oscillator strength due to interband and intersubband optical transitions with the combined effects of hydrostatic pressure and temperature is found. The pressure and temperature induced absorption coefficients as a function of photon energy are investigated in a Ga0.7In0.3N/GaN quantum ring. The results show that the application of pressure leads to blue shift of the resonant peaks of the optical transition whereas the effect of temperature suffers red shift of the resonant peaks.

Electron band bending and surface sensitivity: X-ray photoelectron spectroscopy of polar GaN surfaces

The role of electron band bending and surface sensitivity in determining the core level binding energies by X-ray photoelectron spectroscopy is investigated. A dominating contribution of surface atomic layers to photoemission intensity is confirmed for normal photoemission. The energy of the photoelectron core level peak does not deviate from core level peak energies of electrons photoemitted from the surface atomic layers of the crystal. The higher surface sensitivity regime, achieved e.g. at off-normal photoelectron detection angle, can be used to study the surface potential barrier in just a few topmost atomic layers. In addition, it is demonstrated that core level binding energy measured by angle-resolved X-ray photoelectron spectroscopy reflect the electron attenuation anisotropy. In particular, core level binding energy changes with emission angle and correlates with the forward focusing directions in a crystal. This effect is demonstrated by measuring the polar angle dependence of Ga 3d core levels on clean GaN(0001) and GaN(0001¯) surfaces with a higher and a lower band bending, respectively. The effect is explained by variation of emission depth in a crystal for normal and off-normal photoelectron emission angles.

Solvation Effects for Oxygen Evolution Reaction Catalysis on IrO2(110)

We study the electrochemical interface between rutile IrO2(110) and water to investigate how the inclusion of an explicit solvent influences the stabilities of adsorbed intermediates in the oxygen evolution reaction. Solvent is modeled by explicit nondissociated water molecules, and their structure is determined by a global optimization method. We find that the inclusion of an explicit solvent can significantly affect the geometry of adsorbed intermediates, changing from an interaction with the surface to an interaction with the water bilayer. These water structures consist of stacked octagonal sheets in an ordered network. Solvent stabilization is pronounced for adsorbed *OH and *OOH, which are capable of donating hydrogen bonds. We find little to no change in adsorbate binding energy as the number of layers of solvent is increased from 1 to 3, suggesting a single water bilayer is sufficient to describe the system. With either *O or *OH coadsorbates, the energetics of the reaction pathway are relatively ...

In-situ growth of HfO2 on clean 2H-MoS2 surface: Growth mode, interface reactions and energy band alignment

Room temperature growth of HfO2 thin film on clean 2H-MoS2 via plasma-sputtering of Hf-metal target in an argon/oxygen environment was studied in-situ using x-ray photoelectron spectroscopy (XPS). The deposited film was observed to grow akin to a layer-by-layer growth mode. At the onset of growth, a mixture of sulfate- and sulfite-like species (SOx2− where x=3, 4), and molybdenum trioxide (MoO3), are formed at the HfO2/MoS2 interface. An initial decrease in binding energies for both Mo 3d and S 2p core-levels of the MoS2 substrate by 0.4eV was also observed. Their binding energies, however, did not change further with increasing HfO2 thickness. There was no observable change in the Hf4f core-level binding energy throughout the deposition process. With increasing HfO2 deposition, MoO3 becomes buried at the interface while SOx2− was observed to be present in the film. The shift of 0.4eV for both Mo 3d and S 2p core-levels of the MoS2 substrate can be attributed to a charge transfer from the substrate to the MoO3/SOx2−-like interface layer. Consequently, the Type I heterojunction valence band offset (conduction band offset) becomes 1.7eV (2.9eV) instead of 1.3eV (3.3eV) expected from considering the bulk HfO2 and MoS2 valence band offset (conduction band offset). The formation of these states and its influence on band offsets will need to be considered in their device applications.

Pd–Cu Bimetallic Catalyst on Amidoxime Fiber Realizing an Alternative and High-Efficient Cyanation of Aryl Halide

The reaction of aryl halide cyanation through safe, efficient and stable pathway is of great significance in the industry of fine chemicals. Here, using potassium ferrocyanide and Pd–Cu bimetallic catalyst supported on amidoxime fibers (Cu(I)Pd(II)-AOFs), we propose an alternative reaction pathway for aryl halide cyanation. It shows that a high catalytic activity of cyanation is over 90% for aryl bromides/iodides and about 50% for aryl chlorides at reaction time (2 h), heating reflux in DMAc, in air. The morphology, composition and structure of the prepared catalysts are characterized by SEM, XRD and XPS. The changes of binding energy (N1s O1s Pd3d) show that Pd(II) ions is coordinated with the –NH2/–OH in AOFs, and that Pd(0) and Cu(II) are detected on the surface of AOFs after reaction. These results indicate that CuI makes Pd2+ reduce to Pd0 so as to produce activity central, and that AOFs coordination action is to enhance Pd0 central activity, and that CuI promotes the cyanide ion in potassium ferrocyanide dissociation. A high-efficient cyanation of aryl halide is successfully achieved by the synergistic action with the three actions.

Structural and magnetic properties of Ni nanofilms on Ge(001) by molecular beam epitaxy

Abstract Ni films of 20 nm nominal thickness were grown on Ge(001) substrates by molecular beam epitaxy at several different temperatures from room temperature up to 400 °C. X-ray diffraction and X-ray photoelectron spectroscopy reveal the nucleation of Ni-Ge compounds (NiGe, Ni 2 Ge, Ni 5 Ge 2 ) as well as a departure from the fcc Ni structure exhibited by the films at and beyond a temperature of 100 °C. The binding energy of the Ni 2p peak increases from the RT value (852.7 eV) by 0.5–1.1 eV for the Ni/Ge(001) samples, while the Ge 2p binding energy changes by 0.6–0.7 eV after Ni growth compared to a clean Ge(001) substrate (there is only a ±0.15 eV shift among the samples grown on substrates at higher temperatures). By increasing substrate temperature, we obtained higher intermixing of Ni and Ge, but rather than both Ni and Ge interdiffusing, we find that Ni diffuses further into the germanium with higher substrate temperature, forming increasingly Ni-rich Ni-Ge compounds diluted into the Ge matrix. Based on Magneto-optic Kerr Effect measurements, Ni/Ge(001) grown on substrates at 100 and 200 °C does not exhibit a hysteresis loop, while the samples on 300 and 400 °C substrates show magnetic behavior, which we attribute to the magnetic character of hexagonal Ni 5 Ge 2 (which is determined here for the first time to be a ferromagnetic phase).

The Role of Holes in Borophenes: An Ab Initio Study of Their Structure and Stability with and without Metal Templates

AbstractAn electron‐counting strategy starting from magnesium boride was used to show the inevitability of hexagonal holes in 2D borophene. The number (hole density, HD) and distribution of the hexagonal holes determine the binding energy per boron atom in monolayer borophenes. The relationship between binding energy and HD changes dramatically when the borophene is placed on a Ag(111) surface. The distribution of holes in borophenes on Ag(111) surfaces depends on the temperature. DFT calculations show that aside from the previously reported S1 and S2 borophene phases, other polymorphs may also be competitive. Plots of the electron density distribution of the boron sheets suggest that the observed STM image of an S2 phase corresponds to a sheet with a HD of 2/15 instead of a sheet with a HD of 1/5. The hole density and the hole distribution echo the distribution of vacancies and extra occupancies in complex β‐rhombohedral boron.

The Role of Holes in Borophenes: An Ab Initio Study of Their Structure and Stability with and without Metal Templates.

An electron-counting strategy starting from magnesium boride was used to show the inevitability of hexagonal holes in 2D borophene. The number (hole density, HD) and distribution of the hexagonal holes determine the binding energy per boron atom in monolayer borophenes. The relationship between binding energy and HD changes dramatically when the borophene is placed on a Ag(111) surface. The distribution of holes in borophenes on Ag(111) surfaces depends on the temperature. DFT calculations show that aside from the previously reported S1 and S2 borophene phases, other polymorphs may also be competitive. Plots of the electron density distribution of the boron sheets suggest that the observed STM image of an S2 phase corresponds to a sheet with a HD of 2/15 instead of a sheet with a HD of 1/5. The hole density and the hole distribution echo the distribution of vacancies and extra occupancies in complex β-rhombohedral boron.

External Electric Field Effect on Shallow Donor Impurity States in Zinc-Blende InxGa1−xN/GaN Symmetric Coupled Quantum Dots

Based on the effective-mass approximation and variational procedure, the ground-state donor binding energy in a cylindrical zinc-blende InxGa1-xN/GaN symmetric coupled quantum dots (SCQDs) is investigated in the presence of the external electric field. Numerical results show that the donor binding energy increases firstly until a maximum value, and then it begins to drop quickly in all the cases with decreasing the dot radius. As the thickness of left dot and right dot decreases, the donor binding energy increases monotonically at first, reaches a maximum value, and then drops rapidly for an impurity ion located at the right dot center and the middle barrier center. Moreover, the donor binding energy for an impurity ion located at the center of the left dot is insensitive to the variation of dot thickness for large dot thickness due to the Stark effect. Meanwhile, the impurity position plays an important role on the change of the donor binding energy under the external electric field. In particular, the impurity position corresponding to the peak value of the donor binding energy is shifted toward the left QD with increasing the external electric field strength.

Zintl layer formation during perovskite atomic layer deposition on Ge (001).

Using in situ X-ray photoelectron spectroscopy, reflection high-energy electron diffraction, and density functional theory, we analyzed the surface core level shifts and surface structure during the initial growth of ABO3 perovskites on Ge (001) by atomic layer deposition, where A = Ba, Sr and B = Ti, Hf, Zr. We find that the initial dosing of the barium- or strontium-bis(triisopropylcyclopentadienyl) precursors on a clean Ge surface produces a surface phase that has the same chemical and structural properties as the 0.5-monolayer Ba Zintl layer formed when depositing Ba by molecular beam epitaxy. Similar binding energy shifts are found for Ba, Sr, and Ge when using either chemical or elemental metal sources. The observed germanium surface core level shifts are consistent with the flattening of the initially tilted Ge surface dimers using both molecular and atomic metal sources. Similar binding energy shifts and changes in dimer tilting with alkaline earth metal adsorption are found with density functional theory calculations. High angle angular dark field scanning transmission microscopy images of BaTiO3, SrZrO3, SrHfO3, and SrHf0.55Ti0.45O3 reveal the location of the Ba (or Sr) atomic columns between the Ge dimers. The results imply that the organic ligands dissociate from the precursor after precursor adsorption on the Ge surface, producing the same Zintl template critical for perovskite growth on Group IV semiconductors during molecular beam epitaxy.

The effect of very low water content on the complex dielectric permittivity of clays, sand-clay and sand rocks

The results of measurements of complex relative permittivity of bentonite and clayey sandstone with different degrees of salinity with low moisture are given in the range of temperatures –20° to +105 °C at frequencies from 25 Hz to 1 GHz. It is shown, that even a small amount of water in sandy and sandy-argillaceous rocks causes an increase of the real part of complex relative permittivity at frequencies below 100 Hz. The explanation by linearly-broken dependence of refractive index on moisture is given at its small values. By a dielectric method it is shown that in the process of water film formation on the surface of a mineral, the water molecules binding energy changes. Big distinctions in low-frequency dielectric relaxation times testify to the change of binding energy of molecules of water on the surface of a mineral. Also dependences of relaxation times on temperature are various. The results of dielectric measurements showed a strong influence of the salt on the dielectric permittivity of the clay and clayey sandstone even at a low moisture level.