硫钒铜矿化合物电子结构和电致变色特性的第一原理研究

基于密度泛函的第一原理赝势平面波方法，计算晶体结构、电子结构和光学性质，研究硫钒铜矿化合物Cu₃VS₄、Cu₃NbS₄和Cu₃TaS₄的电子输运及电致变色特性，探讨作为透明半导体材料应用于太阳能电池和电致变色器件的可能性.电子结构的计算表明这类化合物是间接带隙半导体，其电子能带的导带底和价带顶分别位于布里渊区的X点和R点.价带顶的电子本征态主要来自于Cu原子的d电子轨道，而导带底电子态主要来源于VB族元素原子的d电子轨道.能带结构、电荷布居分析、电子局域化函数和光吸收及反射谱的计算表明这些硫钒铜矿化合物属于极性共价半导体，具有较高的电荷迁移率和优良的电致变色特性，可应用于高效电致变色器件.     

埋层界面和空气表面和频光谱信号贡献的调控

本文研究表明通过膜厚控制和表面等离激元增强方法可有效区分隐藏界面和空气表面的和频振动光谱信号. 以氟化钙基底支撑的PMMA薄膜为模型，观察到隐藏界面和空气表面对和频信号贡献的变化. 通过监控羰基和甲基伸缩振动基团，发现薄PMMA膜的和频信号来自PMMA/空气表面的化学基团-CH₂、-CH₃、-OCH₃和C=O，而厚PMMA膜的和频信号则来自基底/PMMA埋层界面的-OCH₃和C=O基团. 随制膜浓度增大，埋层界面C=O基团的取向角从65°下降到43°，且浓度大于或等于0.5 wt%时，取向角等于45°±2°. 相比之下，空气表面C=O的取向角落在21°∽38°之间. 在金纳米棒存在条件下，表面等离激元可以极大地增强和频信号，尤其是来自埋层界面信号.     

Composite host lattices of 4,4′‐sulfonyldibenzoate water/boric acid in two tetrapropylammonium inclusion compounds

Two novel inclusion compounds of 4,4′‐sulfonyldibenzoate anions and tetrapropylammonium cations with different ancillary molecules of water and boric acid, namely bis(tetrapropylammonium) 4,4′‐sulfonyldibenzoate dihydrate, 2C₁₂H₂₈N⁺·C₁₄H₈O₆S²⁻·H₂O ( 1 ), and bis(tetrapropylammonium) 4,4′‐sulfonyldibenzoate bis(boric acid), 2C₁₂H₂₈N⁺·C₁₄H₈O₆S²⁻·2H₃BO₃ ( 2 ), were prepared and characterized using single‐crystal X‐ray diffraction. In the two salts, the host 4,4′‐sulfonyldibenzoic acid molecules, which are converted to the corresponding anions under basic conditions, can be regarded as proton acceptors which link different proton donors of the ancillary molecules of water or boric acid. In this way, an isolated hydrogen‐bonded tetramer is constructed in salt 1 and a ribbon is constructed in salt 2 . The tetramers and ribbons are then packed in a repeating manner to generate various host frameworks, and the tetrapropylammonium guest counter‐ions are contained in the cavities of the host lattices to give the final stable crystal structures. In these two salts, although the host anion and guest cation are the same, the difference in the ancillary small molecules results in different structures, indicating the significance of ancillary molecules in the formation of crystal structures.     

Opposed type double stage cell for Mbar pressure experiment with large sample volume

ABSTRACT

A new opposed type double-stage large volume cell has been developed to compress large volume samples to more than 100?GPa (Mbar) pressure. A pair of second-stage diamond anvils is introduced into the first-stage Paris–Edinburgh press. The double-stage large volume cell allows the generation of ultrahigh pressures using a large culet diameter of the second-stage diamond anvils (diameters of 0.5–1.2?mm). Pressure generation up to 131?GPa has been achieved by using the culet diameter of 0.5?mm. Sample volume of the double-stage large volume cell can be more than ～100 times larger than that of conventional Mbar experiment using a diamond anvil cell. The double-stage large volume cell has a large opening in the horizontal plane for X-ray measurements, which is particularly suited for the multi-angle energy dispersive X-ray diffraction measurement, thus opening a new way of in situ structural determinations of amorphous materials at Mbar pressures.     

Synthesis,Electronic Properties and WOLED Devices of Planar Phosphorus‐Containing Polycyclic Aromatic Hydrocarbons

We describe the synthesis and the physical properties of polyaromatic hydrocarbons (PAHs) containing a phosphorus atom at the edge. In particular, the impact of the successive addition of aromatic rings on the electronic properties was investigated by experimental (UV/Vis absorption, fluorescence, cyclic voltammetry) and theoretical studies (DFT). The physical properties recorded in solution and in the solid state showed that the P‐containing PAHs exhibit properties expected for an emitter in white organic light‐emitting diodes (WOLEDs).     

Free radical polymerization of caffeine‐containing methacrylate monomers

The incorporation of acrylic functionality into caffeine enables the preparation of a vast array of novel thermoplastics and thermosets. A two‐step derivatization provided a novel caffeine‐containing methacrylate monomer capable of free radical polymerization. Copolymers of 2‐ethylhexyl methacrylate and caffeine methacrylate (CMA) allowed for a systematic study of the effect of covalently bound caffeine on polymer properties. ¹H NMR and UV‐vis spectroscopy confirmed caffeine incorporation at 5 and 13 mol %, and SEC revealed the formation of high molecular weight (co)polymers (>40,000 g/mol). CMA incorporation resulted in a multistep degradation profile with initial mass loss closely correlating to caffeine content. Differential scanning calorimetry, rheological, and thermomechanical analysis demonstrated that relatively low levels of CMA increased the glass transition temperature, resulting in higher moduli and elucidating the benefits of incorporating caffeine into polymers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2829–2837     

Hellmann–Feynman connection for the relative Fisher information

The (i) reciprocity relations for the relative Fisher information (RFI, hereafter) and (ii) a generalized RFI–Euler theorem are self-consistently derived from the Hellmann–Feynman theorem. These new reciprocity relations generalize the RFI–Euler theorem and constitute the basis for building up a mathematical Legendre transform structure (LTS, hereafter), akin to that of thermodynamics, that underlies the RFI scenario. This demonstrates the possibility of translating the entire mathematical structure of thermodynamics into a RFI-based theoretical framework. Virial theorems play a prominent role in this endeavor, as a Schrödinger-like equation can be associated to the RFI. Lagrange multipliers are determined invoking the RFI–LTS link and the quantum mechanical virial theorem. An appropriate ansatz allows for the inference of probability density functions (pdf’s, hereafter) and energy-eigenvalues of the above mentioned Schrödinger-like equation. The energy-eigenvalues obtained here via inference are benchmarked against established theoretical and numerical results. A principled theoretical basis to reconstruct the RFI-framework from the FIM framework is established. Numerical examples for exemplary cases are provided.     

Synthesis,Crystal Structure,and Magnetic Properties of a New Dinuclear Iron Complex with Schiff Base Ligand

A new dinuclear iron(Ⅲ) complex has been synthesized and structurally characterized by X-ray crystallography: [FeⅢ2(L)(C6H5COO)(SO4)(CH3OH)2]·CH3CN·CH3OH(1, H3 L = N,N'-bis(salicylidene)-1,3-diamino-2-propanol). Complex 1 belongs to orthorhombic space group Pna21 with a = 11.4400(8), b = 22.9705(2), c = 12.5712(9) , V = 3303.5(4) 3, Z = 4, F(000) = 1576, Dc = 1.531 g·cm–3, Mr = 761.36, μ = 1.007 mm–1, S = 1.014, the final R = 0.0505 and wR = 0.1018. The crystal packing is stabilized by intermolecular O–H···O hydrogen bonds, forming an extended one-dimensional chain structure. The temperature dependence of magnetic susceptibility measurement shows that antiferromagnetic interaction is propagated between the metal centers. Fit as dinuclear arrangement gave parameters of J = 19.7 cm-1, g = 1.89 and R2 = 0.9999.     

The bond ionicity in ANB8−N compounds from maximally localized Wannier functions

The bond ionicity in seventy two A^NB^8−N compounds is investigated according to the recently introduced first-principles ionicity scale, based on the centers of the maximally localized Wannier functions, which has several interesting features. The obtained bond ionicities (q_i) are found to exhibit the expected trends, according to electronegativity arguments. In particular, the bond ionicity in the alkaline-earth oxides increases by going from MgO to BaO. A strong crystal structure dependence of q_i is observed. A critical value of q_i (of 0.91) that separates between the tetrahedrally and octahedrally coordinated systems is inferred directly from the calculated values of q_i. The volume dependence of q_i is investigated for all the considered compounds and found to reduce by volume decrease for most of the studied systems. The adopted ionicity scale is established as a very strong competitor to the most widely accepted Phillips and Pauling ionicity measures.     

Using a Novel and Easy-to-Use Sandwich Structure Device to Evaluate the Cooling Properties of Cool Materials

A number of cool materials have been designed and used in hot weather to minimize the heat coming from sunlight. Traditionally, solar reflectance and infrared emittance were measured to characterize the cooling properties of cool materials. However, these methods could represent the cooling property only indirectly. In this work, a sandwich structure device that can straightforwardly measure the cooling properties of cool materials was designed. Two cool materials, including high-density polyethylene (HDPE) and polyvinyl chloride (PVC), were selected to verify the device. For the purpose of comparison, UV-vis-NIR spectral characterization was also used to evaluate the cooling properties of the selected materials. The results, especially for the HDPE/Green 260 composite sample, which presents much lower solar reflectance but better cooling property, indicated that the cooling properties cannot be entirely represented by only the reflectance or transmittance, and the sandwich structure device was able to make up for this deficiency.