二甲基乙醚低温氧化中关键中间体(HOOCH2OC(=O)H)的分解反应机理

在QCISD(T)/CBS//B3LYP/6-311++G(d,p)方法的基础上计算了DME(二甲基乙醚)低温氧化的中间体HPMF(HOOCH₂OC(=O)H)的分解路径, 并且结合变分过渡态理论及RRKM/主方程求解了温度以及压力依赖的动力学速率. 计算结果表明,除了脱OH的直接解离路径之外,HPMF将经过异构分解生成甲酸及CH₂OO中间体. 新的动力学数据的结果证实了CH₂OO 路径是不容忽略的. 这条分解路径将会降低整个模型的低温氧化活性. 同时从化学本质上去分析了HPMF的化学结构以及电子效应,进一步解释及验证了计算结果的合理性.     

CH2和CH3分子在金属团簇Cun(n=1～6)上吸附性质

以σ-羟基环氧化合物作为模型化合物, 利用密度泛函中B3LYP/6-31G(d,p)的方法研究了三乙基铝促进的环氧化合物的重排还原有机串联反应机理. 根据乙烯消去和六元环重排顺序的不同可有两条可能的反应路径,路径I首先进行的是六元环的收缩重排,而且该步即决速步,能垒为116.62 kJ/mol;路径II中首先发生乙烯的消去然后进行六元环开环重排,开环反应步是该反应路径的决速步,相应的能垒为251.38 kJ/mol,如此高的能垒导致后续反应难于进行. 因此,路径I是更有利的反应路径,与实验结果一致.     

Synthesis and Crystal Structure of α-( N-Protected a mino)β- lactam Derivative of 1 ,5-Benzothiazepine

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Synthesis and Crystal Structure of Dicesium trans Dicarbonatotetraaquomagnesium, Cs_2[Mg(CO_3)_2(H_2O)_4]

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三甲川菁染料敏化TiO2纳米 结构电极的光电化学

The photoelectrochemical behaviors of the TiO₂ nanostructured porous film sensitized by cyanine dye were investigated in this paper.The results showed that the excitaed state level matched the conduction band edge of TiO₂ nanoparticle.Therefore the sensitization of the dye can increase the photocurrent intensity of the TiO₂ nanostructured electrode obviously and results in a red-shift of optical absorption from the ultra-violet region to the visible.As a result,the light-to-electricity conversion efficiency was improved evidently,the maximum value of IPCE has reached 12.1%.     

A Fluorescence Optical Fiber Sensor for Amrinon Using a New Oxazole Compound

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The Elastic Continuum Limit of the Tight Binding Model

The authors consider the simplest quantum mechanics model of solids,the tight binding model,and prove that in the continuum limit,the energy of tight binding model converges to that of the continuum elasticity model obtained using Cauchy-Born rule.The technique in this paper is based mainly on spectral perturbation theory for large matrices.     

酪胺和多巴胺VUV光电离/解离的实验和理论研究

利用同步辐射真空紫外光电离质谱和理论计算对中性酪胺和多巴胺分子的光诱导解离过程进行研究．在较低光子能量下,通过近阈光电离仅得到母体离子信号．当增加光子能量到11.7 eV甚至更高时,从酪胺和多巴胺分别得到四个清晰可辨的碎片离子信号．另外通过测量母体离子的光电离效率曲线,酪胺和多巴胺分子的电离能分别为7.98和7.67 eV(实验误差为±0.05 eV)．结合理论计算建立这两个分子的详细碎裂路径,包括相似的胺乙基消除路径．其中碎片C₇H₈O₂^+·(m/z=124)和C₇H₈O^+·(m/z=108)的生成认为来自McLafferty重排,该过程经历分子内的γ氢迁移诱导的β开裂反应． 另外,C7-C8键直接开裂可以生成CH₂NH₂⁺(m/z=30)碎片离子,并且该过程和McLafferty重排为主要的裂解路径.     

Electronic Instability of Kagome Metal CsV3Sb5 in the 2×2×2 Charge Density Wave State

Recently discovered kagome metals AV₃Sb₅(A = K,Rb,and Cs) provide an ideal platform to study the correlation among nontrivial band topology,unconventional charge density wave(CDW),and superconductivity.The evolution of electronic structures associated with the change of lattice modulations is crucial for understanding of the CDW mechanism,with the combination of angle-resolved photoemission spectroscopy(ARPES)measurements and density functional theory calculations,we invest...