The structural,electronic and magnetic properties of Ag4M and Ag4MCO (M = Sc–Zn) clusters

The structures, spectra and electronic and magnetic properties of Ag₄M and Ag₄MCO (M?=?Sc–Zn) clusters have been studied using density functional theory and CALYPSO structure searching method. Structural searches show that M atoms except Zn tend to occupy the highest coordination position in the ground state Ag₄M and Ag₄MCO clusters. Carbon monoxide is most easily adsorbed on Ag atom of Ag₄Zn and M atom of other Ag₄M. Infrared and Raman spectra, photoabsorption spectra and photoelectron spectra of Ag₄M and Ag₄MCO clusters are forecasted and can be used to identify these clusters from experiment. Analysis of electronic properties indicates that the adsorption of CO on Ag₄M clusters changes the zero vibrational energy (ZPVE) and increases stability of the host clusters. Dopant atoms except for Zn improve the stability of silver cluster. The Ag₄Ni cluster shows high chemical activity and maximum adsorption energy for carbon monoxide. Magnetism calculations reveal that the magnetic moment of Ag₄M (M?=?Mn–Ni) cluster adsorbed by carbon monoxide is decreased by 2 μ_B. The change of magnetic moment makes it possible to be used as a nanomaterial for carbon monoxide detection. Simultaneously, it is found that the adsorption of CO on Ag₄Cu cluster is a physical adsorption.     

Sextic centrifugal distortion constants: interplay of density functional and basis set for accurate yet feasible computations

Quantum-chemical calculations assist the analysis of laboratory spectra, and often provide the only means to determine spectroscopic data that cannot be accessed experimentally. Accurate predictions of vibrational and rotational spectroscopic parameters are required for applications in the field of high-resolution molecular spectroscopy. While the accuracy issue of the quantum-chemical calculation of vibrational properties and of equilibrium structures has been addressed in the literature, the same is not true for centrifugal distortion constants that however play an essential role for the interpretation of remote sensing data. In this work, the performance of several model chemistries, rooted mainly in density functional theory, in computing sextic centrifugal distortion constants is assessed employing a benchmark set of molecules of both atmospheric and astrochemical relevance. The Jensen’s (aug-)pcs-n basis sets, different flavours of Dunning’s triple-ζ basis sets and the SNSD basis set, are employed in conjunction with different functionals, and their predictions are benchmarked against experimental and theoretical data at the coupled cluster level of theory. This study also demonstrates the reliability of the calculation of sextic centrifugal distortion constants within the Gaussian16 rev. B.01 program package. Reliable predictions of the sextic centrifugal distortion constants for the gauche- and trans-conformers of ethyl-mercaptan are also presented.     

Sharper uncertainty principles associated with Lp-norm

Motivated by the well-established phase derivative embedded technique, this study devotes to sharper uncertainty principles related to the L^p-norm type of uncertainty product, giving rise to two kinds of uncertainty inequalities that improve the classical result through providing tighter lower bounds. The conditions that truly reach these better estimates are obtained. Examples and simulations are carried out to verify the correctness of the derived results, and finally, possible applications in time-frequency analysis are also given.     

交错跃迁Hofstadter梯子的量子流相

为玻色Hofstadter梯子模型引入交错跃迁,来扩展模型支持的量子流相.基于精确对角化和密度矩阵重整化群计算发现,无相互作用时,系统中包含横流相、涡旋相和纵流相;横流相来自均匀跃迁时Hofstadter梯子模型的Meissner相,纵流相是交错跃迁时才可见的流相.强相互作用极限下系统的超流区也包含横流相、纵流相和涡旋相,但存在更多的相变级数;超流区的横流相、纵流相之间存在相变但Mott区的不存在,把Mott区的"横、纵流相"称为Mott-均匀相,在Mott区只存在均匀相和涡旋相.跃迁的交错会压缩涡旋相存在的区域,使Mott区最终只剩下均匀相;跃迁的交错不仅能驱动Mott-超流相变,还使磁通的改变也能够驱动系统的Mott-超流相变.对这一系统的研究丰富了磁通系统中的量子流相,同时为研究拓扑流特性提供了模型支持.     

光寻址电位传感器的正交相位检波检测方法

光寻址电位传感器的幅度检测方法易受噪声干扰,灵敏度差,信噪比和精度低,且受调制光源的影响较大,影响检测结果的准确性.为此提出了一种基于正交相位检波的光寻址电位传感器检测方法.该方法是将光寻址电位传感器的输出光电流信号分别与两路正交信号相乘,通过低通滤波提取直流分量并相除,即可得到光寻址电位传感器的输出信号相位信息.与已有的光寻址电位传感器相位检测方法相比,该方法具有算法复杂度低、实时性高的优点.实验研究了调制光源光强对光寻址电位传感器幅度检测和相位检测的影响,对比分析了光寻址电位传感器的传统幅度检测方法与正交相位检波检测方法对pH检测的灵敏度、线性度及信噪比.结果表明,相比于幅度检测方法,调制光源光强对光寻址电位传感器的相位检测影响更小,在频率为10 kHz,pH的范围为1.68~10.01的情况下,相位检测方法比幅度检测方法测得的灵敏度增加了7 mV/pH,精度提高了14.9 mpH,非线性误差减小了0.003%,均方差减少了0.1051×10^-5,信噪比增加了8.2827 dB.该方法特别适用于弱光下的光寻址电位传感器检测.     

Ti0.33WO3电子结构和太阳辐射屏蔽性能第一性原理研究

节能减排已成为当今社会发展的主题,对节约能源、提高太阳能的高效综合利用的新型窗用透明隔热材料的理论设计和研究尤其重要.本文采用基于密度泛函理论的计算方法,研究了六方相三氧化钨Ti掺杂前、后的晶格参数、电子能带结构、形成能和光学性质.研究结果表明,Ti掺杂后晶格体积增大,系统能量降为负值,体系具有更好的稳定性;掺杂后电子能带结构发生很大的变化,但材料仍保持n型电导率;随之,其光学性质也发生改变,掺杂前h-WO3无近红外吸收性能,掺杂后的Ti0.33WO3具有很强的近红外吸收性能.在此基础上研究了Ti掺杂h-WO3前、后的太阳辐射屏蔽性能,掺杂前无太阳辐射屏蔽性能;掺杂后的Ti0.33WO3薄膜具有可见光高透明、近红外屏蔽的性能.计算结果为Ti掺杂h-WO3在窗用透明隔热材料方面的研究提供了理论依据.     

A solvent-governed surface state strategy for rational synthesis of N and S co-doped carbon dots with multicolour fluorescence

ABSTRACT

Multicolour emissive carbon dots (CDs) are widely investigated by virtue of their merits on fluorescent properties. Method on heteroatom doping assisted with various solvents has been proved efficient in achieving multiple-colour-emissive CDs, especially long-wavelength emission. Herein, a synthesis of multicolour-emissive CDs by controlled surface function is reported. By tuning the thermal-pyrolysis temperature and molar ratio of reactants, optimal emission of the resulted CDs gradually shifts from blue to yellow light with the assistance of different solvents. According to the emissive relationship dependent on excitation, fluorescence lifetimes, and FT-IR of these CDs, the different surface states participated with S and N elements on the surface of carbogenic core govern fluorescent colours of the CDs. In terms of the applications, blue CDs (B-CDs) exhibits high sensitivity for ion detections of Ag⁺ and Fe³⁺, which is further illustrated to have different quenching mechanisms each other because that these ions have the affinity interaction with different surface groups of the CDs. Moreover, blue and yellow CDs solutions are mixed with PVP water solution to fabricate white-light CDs/PVP film, which exhibits stable fluorescence with a CIE coordinate of (0.32, 0.33) and endows these CDs as potentially fluorescent nanomaterial in the solid state lighting field.     

Amorphous silicon hexaboride at high pressure

ABSTRACT

We investigate the pressure-induced structural phase transformation of amorphous silicon hexaboride (a-SiB₆) using a constant pressure first principles approach. a-SiB₆ is found to undergo a gradual phase transformation to a high-density amorphous phase (HDA) in which the average coordination number of both B and Si atoms is about 6. The HDA phase consists of differently coordinated motifs ranging from 4 to 8. B₁₂ icosahedra are found to persist during compression of a-SiB₆ and the structural modifications primarily occur around Si atoms and in the regions linking pentagonal pyramid-like configurations to each other. Upon pressure release, an amorphous structure, similar to the uncompressed one, is recovered, indicating a reversible amorphous-to-amorphous phase change in a-SiB_6. When the electronic structure is considered, the HDA phase is perceived to have a wider forbidden band gap than the uncompressed one.     

基于化学学科认知障碍突破的中考复习教学实践* ——以“二氧化碳的性质”为例

分析学生对二氧化碳的3个典型学科认知障碍,以“二氧化碳的捕捉”为情境,通过“尝试捕捉二氧化碳”“谁在捕捉二氧化碳”“捕捉背后的原理”等3个主要环节,实现对学科认知障碍的突破,展示了一种新的中考复习教学思路。     

电镀铜实验中镀层性质及其影响因素的探究*

电镀实验是电解原理应用的重要案例,通过实验不仅要获得定性的感性认知,还应该获得定量的理性数据。针对电镀铜实验,通过改变铜离子浓度、pH、电解时间、电解电压和电解温度等因素,探究其对镀层厚度、均匀性和致密性等性质的影响,在电解原理的基础上分析其形成机制,从而确定了电镀铜较适宜的操作条件,以此为学生开展电镀实验提供参考案例与研究思路。