Electronic structure and absolute band edge position of tetragonal AgInS2 photocatalyst: A hybrid density functional study

Energy bands, effective mass of carriers, absolute band edge positions and optical properties of tetragonal AgInS₂ were calculated using a first-principles approach with the exchange correlation described by B3LYP hybrid functional. The results indicate that tetragonal AgInS₂ has a direct band gap of 1.93 eV, which reproduce well experimental value. Calculated effective masses of electrons and holes are both small which are beneficial to separation and migration of electron and hole pairs. This implies that AgInS₂ has good photocatalytic performance. The calculated optical characteristics indicate that AgInS₂ has a slight anisotropy for both the real and imaginary parts of the dielectric function and exhibits large optical absorption in the visible light region. Furthermore, the calculated band edge positions in (100), (010) and (001) surfaces indicate that tetragonal AgInS₂ is beneficial to the reduction and oxidation of water to hydrogen and oxygen under visible light irradiation.     

Ab initio calculations of the NO2 fission for CL-20 conformers

NO₂ fission is regarded to be the most important initial decomposition process of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20). In this study, four CL-20 conformers based on the ε-CL-20 were obtained after the optimization at m062x/cc-pvtz level, and the bond length, bond order and bond dissociation energy of the N-N bonds were examined to investigate the stability of these bonds. In addition, the rate constants and activation energy of the NO₂ fission were evaluated using the microcanonical variational transition state theory (μVT). The calculation results have shown that N-N bonds in the case of pseudo-equatorial and axial of nitro groups are the most stable and the least stable, respectively, by evaluating the bond length, bond order and minimum energy path (MEP). The NO₂ fission rate constants are affected by not only the stability of N-N bonds but also the repulsion forces from the other nitro groups, and the fission process for pseudo-equatorial positioning of nitro groups is easier to be accelerated due to the increase of the repulsion forces. The decomposition of CL-20 conformer may mainly originate from the fission of the pseudo-equatorial positioning of nitro groups, especially for CL-20 III conformer because of the significant low activation energy.     

[N_2]_2二聚物激光介质研究

理论上通过从头算法 (abinitio)计算强相互作用的N2 分子二聚物可能存在的 6种点群构型的势能曲线 ,证明N2 分子二聚物以D2h 对称群构型存在 ,且存在电偶极允许的类准分子跃迁a1B2 g →a1B3u,并计算了a1B2 g →a1B3u 跃迁的荧光谱。估算了N2 分子二聚物 ( 3 3 6 2 1nm)的小信号增益系数。利用微波 ( 2 45GHz)激励高纯氮 ,实验观测了N2 分子二聚物的系列荧光谱带 ,并利用放大自发辐射 (ASE)法测量N2 分子二聚物 ( 3 3 6 2 1nm)的小信号增益系数 ,在误差范围内与理论估算基本一致。最后从理论上估算了N2 分子二聚物激光振荡的输出功率。     

光学元件吸收测量

采用量热法测量了光学元件的吸收,分析了元件表面反射对测量的影响,并测量了GaAs基片和GaAs高反镜的吸收,分析了测量误差。     

Atomistic Origin of the Enhanced Crystallization Speed and n‐Type Conductivity in Bi‐doped Ge‐Sb‐Te Phase‐Change Materials

Phase‐change alloys are the functional materials at the heart of an emerging digital‐storage technology. The GeTe‐Sb₂Te₃ pseudo‐binary systems, in particular the composition Ge₂Sb₂Te₅ (GST), are one of a handful of materials which meet the unique requirements of a stable amorphous phase, rapid amorphous‐to‐crystalline phase transition, and significant contrasts in optical and electrical properties between material states. The properties of GST can be optimized by doping with p‐block elements, of which Bi has interesting effects on the crystallization kinetics and electrical properties. A comprehensive simulational study of Bi‐doped GST is carried out, looking at trends in behavior and properties as a function of dopant concentration. The results reveal how Bi integrates into the host matrix, and provide insight into its enhancement of the crystallization speed. A straightforward explanation is proposed for the reversal of the charge‐carrier sign beyond a critical doping threshold. The effect of Bi on the optical properties of GST is also investigated. The microscopic insight from this study may assist in the future selection of dopants to optimize the phase‐change properties of GST, and also of other PCMs, and the general methods employed in this work should be applicable to the study of related materials, for example, doped chalcogenide glasses.     

Formation Energies of the Lithium Intercalations in MoS2

First-principles calculations have been performed to study the lithium intercalations in MoS2. The formation energies, changes of volumes, electronic structures and charge densities of the lithium intercalations in MoS2 are presented. Our calculations show that during lithium intercalations in MoS2, the lithium intercalation formation energies per lithium atom are between 2.5 eV to 3.0 eV. The volume expansions of MoS2 due to lithium intercalations are relatively small     

3- Instead of 4-helix formation in a de novo designed protein in solution revealed by small-angle X-ray scattering

De novo design and chemical synthesis of proteins and their mimics are central approaches for understanding protein folding and accessing proteins with novel functions. We have previously described carbohydrates as templates for the assembly of artificial proteins, so-called carboproteins. Here, we describe the preparation and structural studies of three alpha-helical bundle carboproteins, which were assembled from three different carbohydrate templates and one amphiphilic hexadecapeptide sequence. This heptad repeat peptide sequence has been reported to lead to 4-alpha-helix formation. The low resolution solution structures of the three carboproteins were analyzed by means of small-angle X-ray scattering (SAXS) and synchrotron radiation circular dichroism (SRCD). The ab initio SAXS data analysis revealed that all three carboproteins adopted an unexpected 3+1-helix folding topology in solution, while the free peptide formed a 3-helix bundle. This finding is consistent with the calculated alpha-helicities based on the SRCD data, which are 72 and 68 % for two of the carboproteins. The choice of template did not affect the overall folding topology (that is for the 3+1 helix bundle) the template did have a noticeable impact on the solution structure. This was particularly evident when comparing 4-helix carboprotein monomers with the 2x2-helix carboprotein dimer as the latter adopted a more compact conformation. Furthermore, the clear conformational differences observed between the two 4-helix (3+1) carboproteins based on D-altropyranoside and D-galactopyranoside support the notion that folding is affected by the template, and subtle variations in template distance-geometry design may be exploited to control the solution fold. In addition, the SRCD data show that template assembly significantly increases thermostability.     

Micro scale fracture strength of grains and grain boundaries in polycrystalline La-doped β-Si3N4 ceramics

Micro scale fracture strength of grains and grain boundaries in polycrystalline La-doped β-Si₃N₄ ceramics were investigated and compared with theoretically predicted values. The fracture behaviour of SiO₂-La₂O₃ intergranular glassy phase (IGP) between β-Si₃N₄ grains was modelled by ab initio simulations. Microcantilevers were FIB-milled both from polycrystalline regions and single grains of β-Si₃N₄ and were tested in bending using a nanoindenter. The fracture strength of β-Si₃N₄ grains which fractured at fixing was 10.6 ± 0.8 GPa while the strength of the beams that failed at defects was 5.9 ± 2.3 GPa. Polycrystalline β-Si₃N₄ samples showed intergranular fracture with decreasing strength values in the range of 2.9 ± 0.4 – 2.1 ± 0.5 GPa. The comparison of single grain results with theoretical values in the literature revealed a correlation between theoretical and experimental results, which was used to convert our ab initio simulations from subnano to micro size samples. The converted strength for IGP showed quantitative agreement with micro-bending experiments.     

Friction and a Tribochemical Reaction between Ice and Hexagonal Boron Nitride: A Theoretical Study

Friction between ice-Ih and hexagonal boron nitride (h-BN) has been determined by periodic ab initio calculations. Surfaces of ice-Ih and h-BN were brought into sliding contact, and the interaction energies were calculated as a function of interplanar distance and lateral displacement of the surfaces. The friction between the surfaces was calculated from the interaction energies, producing a friction coefficient of 0.140. Friction is further influenced at high loads by a tribochemical reaction between ice-Ih and h-BN.