非晶态固体的结构可以决定性能吗?

晶态固体的力学性能与塑性变形主要由结构缺陷, 比如位错的运动决定. 而在非晶态固体中结构如何决定性能, 仍然是固体力学、材料学和凝聚态物理学共同关心但尚未解决的核心问题之一.传统材料学研究的经典范式为"结构决定性能". 遵循这一信条, 已经有大量的实验表征与理论、模拟研究, 尝试将非晶态固体的某种结构特征与性能建立一一对应关系. 但是, 科学界对于非晶固体结构-性能关系成立与否, 以及背后隐藏的规律知之甚少. 本文针对非晶态固体的变形机制以及其微结构特征, 基于分子动力学模拟, 定量评估短程简单结构与中长程复杂结构在决定非晶态固体动力学性能方面的效用. 通过海量抽样每种具体玻璃结构的激活能(标识激发难易程度), 尝试将结构参数与激活能建立定量关系, 从而揭示出非晶态固体结构-性能关系的隐藏主控因素为结构的空间关联, 受限比几何结构本身更关键. 只有某种结构在空间上呈现亚纳米级的空间关联长度, 这种完备结构才有可能有效地决定非晶态固体的力学性能, 而短程简单结构则无效. 进一步, 给出了评价非晶态固体结构预测性能有效性的普适定量方法, 为建立广义无序物质的结构-性能关系提供了筛选准则.      

DFT modeling of indoline spiropyrans with a cationic substituent in the gas phase

Isomeric forms of indoline spiropyrans show unusual behavior compared with similar compounds, according to experimental data. DFT modeling for gas phase was made to consider the simplest case without environmental effects, which revealed the intramolecular reasons for occurrence of ring opening reaction depending on the particular structure of the compound. The questions of charge redistributions, the changes of geometry and chemical bonds in the structures are also discussed.     

Metal-Mediated Directional Capping of Rod-Packing Metal–Organic Frameworks

Two new rod-packing metal–organic frameworks (RPMOF) are constructed by regulating the in situ formation of the capping agent. In CPM-s7, carboxylate linkers extend 1D manganese-oxide chains in four additional directions, forming 3D RPMOF. The substitution of Mn²⁺ with a stronger Lewis acidic Co²⁺, leads to an acceleration of the hydrolysis-prone sulfonate linker, resulting in presence of sulfate ions to reduce two out of the four carboxylate-extending directions, and thus forming a new 2D rod-packing CPM-s8. Density functional theory calculations and magnetization measurements reveal ferrimagnetic ordering of CPM-s8, signifying the potential of exploring 2D RPMOF for effective low-dimensional magnetic materials.     

Visible-Light Augmented Lithium Storage Capacity in a Ruthenium(II) Photosensitizer Conjugated with a Dione-Catechol Redox Couple

Controlling redox activity of judiciously appended redox units on a photo-sensitive molecular core is an effective strategy for visible light energy harvesting and storage. The first example of a photosensitizer - electron donor coordination compound in which the photoinduced electron transfer step is used for light to electrical energy conversion and storage is reported. A photo-responsive Ru-diimine module conjugated with redox-active catechol groups in [Ru(II)(phenanthroline-5,6-diolate)₃]⁴⁻ photosensitizer can mediate photoinduced catechol to dione oxidation in the presence of a sacrificial electron acceptor or at the surface of an electrode. Under potentiostatic condition, visible light triggered current density enhancement confirmed the light harvesting ability of this photosensitizer. Upon implementation in galvanostatic charge-discharge of a Li battery configuration, the storage capacity was found to be increased by 100 %, under 470 nm illumination with output power of 4.0 mW/cm⁻². This proof-of-concept molecular system marks an important milestone towards a new generation of molecular photo-rechargeable materials.     

Improved Reversible Zinc Storage Achieved in a Constitutionally Crystalline-Stable Mn(VO3)2 Nanobelts Cathode

Rechargeable zinc-ion batteries (ZIBs) are potential for grid-scale applications owing to their safety, low price, and available sources. The development of ZIBs cathode with high specific capacity, wide operating voltage window and stable cyclability is urgently needed in next-generation commercial batteries. Herein, we report a structurally crystalline-stable Mn(VO₃)₂ nanobelts cathode for ZIBs prepared via a facile hydrothermal method. The as-synthesized Mn(VO₃)₂ exhibited high specific capacity of 350 mAh g⁻¹ at 0.1 A g⁻¹, and maintained a capacity retention of 92 % after 10,000 cycles at 2 A g⁻¹. It also showed good rate performance and obtained a reversible capacity of up to 200 mAh g⁻¹ after 600 cycles at 0.2 A g⁻¹ under −20 °C. The electrochemical tests suggest that Mn(VO₃)₂ nanobelts impart fast Zn²⁺ ions migration, and the introduction of manganese atoms help make the structures more indestructible, leading to a good rate performance and prolonged cycle lifespan.     

Mechanism of BPh3-Catalyzed N-Methylation of Amines with CO2 and Phenylsilane: Cooperative Activation of Hydrosilane

BPh₃ catalyzes the N-methylation of secondary amines and the C-methylenation (methylene-bridge formation between aromatic rings) of N,N-dimethylanilines or 1-methylindoles in the presence of CO₂ and PhSiH₃; these reactions proceed at 30–40 °C under solvent-free conditions. In contrast, B(C₆F₅)₃ shows little or no activity. ¹¹B NMR spectra suggested the generation of [HBPh₃]⁻. The detailed mechanism of the BPh₃-catalyzed N-methylation of N-methylaniline ( 1 ) with CO₂ and PhSiH₃ was studied by using DFT calculations. BPh₃ promotes the conversion of two substrates (N-methylaniline and CO₂) into a zwitterionic carbamate to give three-component species [Ph(Me)(H)N⁺CO₂⁻⋅⋅⋅BPh₃]. The carbamate and BPh₃ act as the nucleophile and Lewis acid, respectively, for the activation of PhSiH₃ to generate [HBPh₃]⁻, which is used to produce key CO₂-derived species, such as silyl formate and bis(silyl)acetal, essential for the N-methylation of 1 . DFT calculations also suggested other mechanisms involving water for the generation of [HBPh₃]⁻ species.     

Spectroscopic properties and bond dissociation energies of PbX,PbX±, PbX2 and PbX2± (X ​= ​F,Cl, Br,I)

Ab initio calculations have been performed to investigate some of the spectroscopic properties, like geometry, frequency, electron affinity, ionization potential and finally adiabatic bond dissociation energies (BDEs) of lead monohalides, lead dihalides and their ions viz. PbX, PbX^±, PbX₂, $\mathrm{P}\mathrm{b}{\mathrm{X}}_{\mathrm{2}}^{\pm }$ (X ?= ?F, Cl, Br, I) in their ground state at the QCISD(T)//MP2 level of theory using correlation consistent basis sets. For the validation of MP2 optimized geometry and frequency, we further obtained geometry and frequency of all the neutral and ionic systems using QCISD(T) method with the same basis sets. The BDEs of PbX₂ molecules are calculated using the BDEs of $\mathrm{P}\mathrm{b}{\mathrm{X}}_{\mathrm{2}}^{\pm }$ ions and taking ionization potential and electron affinity of various systems. The calculated values are found in good agreement with the available data. Most of the data for ionic systems are reported first time in literature.     

2,3-Disubstituted Fluorene Scaffold for Efficient Green Phosphorescent Organic Light-Emitting Diodes

Fluorene is a classic three-membered polycyclic aromatic hydrocarbon, and it has been widely used in optoelectronic devices. Here we explore a simple and efficient strategy for the derivatization at the 2- and 3- positions in fluorene unit. By introducing different types of substituents, we design two pairs of 2,3-disubstituted fluorene isomers and use them as host materials for phosphorescent organic light-emitting diodes (PHOLEDs). The green PHOLEDs hosted by these fluorene derivatives realize high external quantum efficiencies (EQE) over 20 % with low efficiency roll-off. Particularly, the devices hosted by 2TRz3TPA and 2TPA3TRz achieve nearly 24 % EQE and 104 lm W⁻¹ power efficiency. These results clearly demonstrate that the 2,3-disubstituted fluorene platforms are potentially useful for constructing host materials.     

AgAlSe2晶体高压相变的第一性原理研究

基于密度泛函理论,采用广义梯度近似法,研究了黄铜矿结构AgAlSe₂在高压下的晶体结构、晶格动力学稳定性与电子结构.结果显示:在0 GPa时AgAlSe₂的晶格参数与实验值吻合,在13.9 GPa附近,质量密度、Se-Ag键长、Se-Al键长、晶格常数a突然增大,相对晶胞体积V/V₀、晶格常数c突然减小,声子谱出现虚频,结构变得不稳定,带隙发生突变,数值呈减小趋势.表明AgAlSe₂晶体在13.9 GPa附近发生结构相变.该研究为AgAlSe₂晶体在理论上所能承受的高压提供信息支撑.