M2B7-(M=Mg,Zn)团簇的双重芳香性促进Mg-Mg和Zn-Zn单键的形成

本文使用密度泛函理论设计了两个无需配体的具有Mg-Mg和Zn-Zn单键的团簇Mg₂B₇^-和Zn₂B₇^-. 这两种团簇的全局能量最低构型均以M₂²⁺(B₇^3-)的形式存在，其中M-M单键处于准平面六边形形状的B₇部分的上方. 化学键分析证实了这些团簇中Mg-Mg和Zn-Zn单键的存在，这些单键是在异常稳定的B₇^3-的驱动下生成的. 该B₇^3-部分同时具有σ和π双重芳香性. 计算得到Mg₂B₇^-和Zn₂B₇^-的垂直跃迁能分别为2.79 eV和2.94 eV.     

窄线宽光纤激光器在1030 nm波段实现3 kW近衍射极限输出

基于大模场面积掺镱光纤搭建了全光纤1030 nm高功率窄线宽光纤激光主振荡功率放大系统,实现了3004 W的最高功率输出,斜率效率69.27%,是目前报道的输出功率最高的1030 nm波段近衍射极限光纤激光器。最高输出功率时,x,y方向的光束质量因子分别为1.169,1.174,3 dB光谱宽度为0.18 nm,放大自发辐射抑制比达到37 dB。     

利用改进的Gamow-like模型研究原子核的α衰变和质子放射性

通过引入离心势和静电屏蔽效应对Gamow-like模型进行了改进，并将其用于α衰变和质子放射性研究，发现改进的Gamow-like模型能更好地符合实验数据。另外，还利用改进的Gamow-like模型预言了16个丰质子核的质子放射性的半衰期以及7个$Z=120$超重核素($^{296-308}120$)α衰变链上原子核的α衰变的半衰期，为将来在大科学装置上合成和鉴别这些新核素提供重要的理论参考。     

Quadratic sums of Gaussian q-binomial coefficients and Fibonomial coefficients

The Ramanujan Journal - In this paper we evaluate quadratic sums of Gaussian q-binomial coefficients with two additional parameters. We obtain a general summation theorem using a combination of...     

One-step synthesis of novel flower-like Sn-doped ZnO architectures with enhanced photocatalytic activity

A facile hydrothermal method to synthesize flower-like Sn-doped ZnO (FLSn-ZnO) nanostructures is described. The obtained hierarchical architectures of FLSn-ZnO are found to be assembled with abundant regular-shaped nanosheets and nanoparticles. A possible formation mechanism is proposed on the base of a series of control experiments. The tests show that FLSn-ZnO architectures exhibit higher photocatalytic activity in the degrading Rhodamine B and tetracycline aqueous solution than pure ZnO under UV-light irradiation. And photocurrent response and photoluminescence of ZnO and FLSn-ZnO demonstrates that in photocatalytic performance, the latter is higher.     

13C chemical shift tensors in MOF α-Mg3(HCOO)6: Which component is more sensitive to host-guest interaction?

Metal–organic frameworks (MOFs) are a class of important porous materials with many current and potential applications. Their applications almost always involve the interaction between host framework and guest species. Therefore, understanding of host–guest interaction in MOF systems is fundamentally important. Solid-state NMR spectroscopy is an excellent technique for investigating host–guest interaction as it provides information complementary to that obtained from X-ray diffraction. In this work, using MOF α-Mg₃(HCOO)₆ as an example, we demonstrated that ¹³C chemical shift tensor of organic linker can be utilized to probe the host–guest interaction in MOFs. Obtaining ¹³C chemical shift tensor components (δ₁₁, δ₂₂, and δ₃₃, where δ₁₁ ≥ δ₂₂ ≥ δ₃₃) in this MOF is particularly challenging as there are six coordinatively equivalent but crystallographically non-equivalent carbons in the unit cell with very similar local coordination environment. Two-dimensional magic-angle-turning experiments were employed to measure the ¹³C chemical shift tensors of each individual crystallographically non-equivalent carbon in three microporous α-Mg₃(HCOO)₆ samples with different guest species. The results indicate that the δ₂₂ component (with its direction approximately being co-planar with the formate anion and perpendicular to the C−H bond) is more sensitive to the adsorbate molecules inside the MOF channel due to the weak C−H···O hydrogen bonding or the ring current effect of benzene. The ¹³C isotropic chemical shift, on the other hand, seems much less sensitive to the subtle changes in the local environment around formate linker induced by adsorption. The approach described in this study may be used in future studies on host–guest interaction within MOFs.     

Predicting polycyclic aromatic hydrocarbon formation with an automatically generated mechanism for acetylene pyrolysis

Using Reaction Mechanism Generator (RMG), we have automatically constructed a detailed mechanism for acetylene pyrolysis, which predicts formation of polycyclic aromatic hydrocarbons (PAHs) up to pyrene. To improve the data available for formation pathways from naphthalene to pyrene, new high‐pressure limit reaction rate coefficients and species thermochemistry were calculated using a combination of electronic structure data from the literature and new quantum calculations. Pressure‐dependent kinetics for the CH potential energy surface calculated by Zádor et al. were incorporated to ensure accurate pathways for acetylene initiation reactions. After adding these new data into the RMG database, a pressure‐dependent mechanism was generated in a single RMG simulation which captures chemistry from C to C. In general, the RMG‐generated model accurately predicts major species profiles in comparison to plug‐flow reactor data from the literature. The primary shortcoming of the model is that formation of anthracene, phenanthrene, and pyrene are underpredicted, and PAHs beyond pyrene are not captured. Reaction path analysis was performed for the RMG model to identify key pathways. Notable conclusions include the importance of accounting for the acetone impurity in acetylene in accurately predicting formation of odd‐carbon species, the remarkably low contribution of acetylene dimerization to vinylacetylene or diacetylene, and the dominance of the hydrogen abstraction CH addition (HACA) mechanism in the formation pathways to all PAH species in the model. This work demonstrates the improved ability of RMG to model PAH formation, while highlighting the need for more kinetics data for elementary reaction pathways to larger PAHs.     

One-pot,one-step,and selective terpolymerization of ethylene oxide,propylene oxide,and COS to copoly(thioether)s with tunable thermal properties

Facile construction of sulfur-rich polymers using readily available raw chemicals is an area aggressively pursued but challenging. Herein we use common feedstocks of ethylene oxide (EO), propylene oxide (PO), and carbonyl sulfide (COS) to synthesize copoly(thioether)s which are traditionally produced from unpleasant and difficult to store episulfides. In this protocol, the EO/COS coupling selectively generates a pure poly(ethylene sulfide) (PES) with melting temperature (T_m) values up to 172°C and high yields up to 98%. The EO/PO/COS terpolymerization leads to the incorporation of soft poly(propylene sulfide) (PPS) and hard PES segments together, affording a random PES-co-PPS copoly(thioether) with the complete consumption of EO and PO. Additionally, by simply varying the EO/PO feeding ratio, the obtained copoly(thioether)s possess tunable thermal properties, T_m values in the range of 76–144°C, and excellent solubility. These copolymerizations are conducted in one-pot/one-step at industrially favored reaction temperatures of 100–120°C using catalysts of common organic bases, suggesting a facile and practical manner. Especially, the copoly(thioether) exhibits high refractive indices up to 1.68 owing to its high sulfur content, suggesting a broad application prospect in optical materials.