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1.
《中国物理 B》2021,30(5):56501-056501
Thermal expansion control is always an obstructive factor and challenging in high precision engineering field. Here,the negative thermal expansion of Nb F_3 and Nb OF_2 was predicted by first-principles calculation with density functional theory and the quasi-harmonic approximation(QHA). We studied the total charge density, thermal vibration, and lattice dynamic to investigate the thermal expansion mechanism. We found that the presence of O induced the relatively strong covalent bond in Nb OF_2, thus weakening the transverse vibration of F and O in Nb OF_2, compared with the case of Nb F_3.In this study, we proposed a way to tailor negative thermal expansion of metal fluorides by introducing the oxygen atoms.The present work not only predicts two NTE compounds, but also provides an insight on thermal expansion control by designing chemical bond type. 相似文献
2.
《Mendeleev Communications》2022,32(4):467-470
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. 相似文献
3.
Yaoli Wang Yan Liang Huixiang Sheng Jin Wang Junjie Wang Shunhao He Mengdan Guan Yaqi Chen Prof. Gang Lu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(2):e202103709
Surface plasmon can trigger or accelerate many photochemical reactions, especially useful in energy and environmental industries. Recently, molecular adsorption has proven effective in modulating plasmon-mediated photochemistry, however the realized chemical reactions are limited and the underlying mechanism is still unclear. Herein, by using in situ dark-field optical microscopy, the plasmon-mediated oxidative etching of silver nanoparticles (Ag NPs), a typical hot-hole-driven reaction, is monitored continuously and quantitatively. The presence of thiol or thiophenol molecules is found essential in the silver oxidation. In addition, the rate of silver oxidation is modulated by the choice of different thiol or thiophenol molecules. Compared with the molecules having electron donating groups, the ones having electron accepting groups accelerate the silver oxidation dramatically. The thiol/thiophenol modulation is attributed to the modulation of the charge separation between the Ag NPs and the adsorbed thiol or thiophenol molecules. This work demonstrates the great potential of molecular adsorption in modulating the plasmon-mediated photochemistry, which will pave a new way for developing highly efficient plasmonic photocatalysts. 相似文献
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Wacker oxidation is an industry-adopted process to transform olefins into value-added epoxides and carbonyls. However, traditional Wacker oxidation involves the use of homogeneous palladium and copper catalysts for the olefin addition and reductive elimination. Here, we demonstrated an ultrahigh loading Cu single atom catalyst(14% Cu, mass fraction) for the palladium-free Wacker oxidation of 4-vinylanisole into the corresponding ketone with N-methylhydroxylamine hydrochloride as an additive under mild conditions. Mechanistic studies by 18O and deuterium isotope labelling revealed a hydrogen shift mechanism in this palladium-free process using N-methylhydroxylamine hydrochloride as the oxygen source. The reaction scope can be further extended to Kucherov oxidation. Our study paves the way to replace noble metal catalysts in the traditional homogeneous processes with single atom catalysts. 相似文献
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In this paper, a quantum cascade laser (QCL) design is proposed based on GaAs/AlGaAs material system, which simultaneously operates at three widely separated wavelengths ( and ). In the design, all the wavelength radiations are achieved by the engineering of the electronic spectrum via the quantum-well widths and the applied electric field in a single active region within a same waveguide. The mid-infrared (mid-IR) wavelengths are obtained by adoption a dual-upper-state active region, and the proposed design aims to use both the mid-IR radiations as the coherent deriving fields to populate the upper THz lasing state to aid the THz-laser population inversion via optical pumping instead of direct electrical injection. A detailed analysis of electronic transport in the structure is carried out using a multi-level rate-equation model. The results show that the proposed structure offers an alternative approach to room temperature THz generation in QCLs. 相似文献
10.
Bohuai Xiao Jianqiao Dong Zhiye Wang Xu Wang Mingjun Sun Jing Guo Gongming Qian Yunchuan Li Shuai Chang 《Chemphyschem》2022,23(7):e202100833
One important prerequisite for the fabrication of molecular functional device strongly relies on the understanding the conducting behaviors of the metal-molecule-metal junction that can respond to an external stimulus. The model Lewis basic molecule 4,4′-(pyridine-3,5-diyl)dibenzonitrile (DBP), which can react with Lewis acid and protic acid, was synthesized. Then, the molecular conducting behavior of DBP, DBP-B(C6F5)3, and DBP-TfOH (DBP-B(C6F5)3, and DBP-TfOH were produced by Lewis acid and protonic acid treatment of DBP) was researched and compared. Given that their identical physical paths for DBP, DBP-B(C6F5)3, and DBP-TfOH to sustain charge transport, our results indicate that modifying the molecular electronic structure, even not directly changing the conductive physical backbone, can tune the charge transporting ability by nearly one order of magnitude. Furthermore, the addition of another Lewis base triethylamine (of stronger alkaline than DBP), to Lewis acid-base pair reverts the electrical properties back to that of a single DBP junction, that is constructive to propose a useful but simple strategy for the design and construction of reversible and controllable molecular device based on pyridine derived molecule. 相似文献