PrBa2Cu3O6+x(x=1,0.3)中Pr价态随氧含量的变化

报道了陶瓷和c轴取向薄膜 PrBa₂Cu₃O_6+x(x=1,0.3)材料的红外反射光谱，通过比较区分出该材料的沿着c轴振动和沿着a-b平面振动的声子模，PrBa₂Cu₃O_6+x和RBa₂Cu₃O_6+x(x=1-0,R=Y和稀土元素)有类似的晶体结构，分析和比较它们的声子谱，其中尤其是Pr和Y,Pr和其它稀土元素 关键词：     

Theoretical Insights into the Substituent Effects on the Fluorescence of Boron Complexes of 2-(Benzothiazol-2-yl)phenols: a Quantum Mechanics Study

The performance of organic fluorescent materials can be improved by chemical substitutions with auxochrome groups such as amino to increase solubility, alter emitting color, or modify film quality. The complex 6,6-difluoro-6-bora-5-oxa-11-thia-6 a-aza-benzo[a]fluorine(BOBTP) and its derivatives, which possess excellent luminescent property at room temperature, were theoretically simulated by density functional theory. The geometries of the ground state and the first excited state of BOBTPs complexes were investigated and their bond parameters were obtained. Further, these bond parameters are compared with each other, and the computational wavelengths of maximum absorption and emission of studied complexes match up with the experimental values. It was found that amino substituent bonding to appropriate positions of BOBTP can reduce the reorganization energy significantly, which is ascribed to electron-donating effect of the amino group. The reorganization energy also plays an important role in the fluorescence quantum yield of all the BOBTPs. In particular, the radiative decay of complexes 3 and 4 is dominant due to the smaller reorganization energies, so their fluorescence quantum yield is almost 1, on the contrary the non-radiative decay and intersystem crossing rate of both the 1 and 2 can not be ignored for the larger reorganization energies, and the corresponding fluorescence quantum yields were calculated when the radiative decay rate(kr) and nonradiative decay rate(k(nr)) were taken into account.     

5,7′-(亚甲胺基)-二-8-羟基喹啉及其金属有机配合物的密度泛函和自然键轨道及电子密度拓扑理论研究

采用密度泛函理论, 在B3LYP/6-31G水平上对5,7′-(亚甲胺基)-二-羟基喹啉及其3种金属M(M=Zn, Mg, Be)有机配合物M(5,7′-Iminomethylq2)2的结构进行了全优化, 并用TDDFT方法计算了吸收光谱. 同时, 利用自然键轨道理论(NBO)和电子密度拓扑分析(AIM)方法对分子内氢键进行了分析. 结果表明, 光谱计算值与实验值基本符合, 该类化合物均具有较大的电子亲和能, 改变中心金属原子对配合物吸收光谱性质的影响不大. 和5,7′-Iminomethylq2相比, M(5,7′-Iminomethylq2)2的吸收光谱产生明显红移. 5,7′-Iminomethylq2及其M(5,7′-Iminomethylq2)2分子内存在较强的氢键, 可形成三元环, 五元环和六元环. 分子内氢键的存在使分子的稳定性增加.     

硅的间接跃迁双光子吸收系数谱

利用皮秒Nd:YAG脉冲激光器作为激发光源,测量出光子能量介于1.36 μm (0.912 eV)—1.80 μm (0.689 eV)之间的硅间接跃迁双光子吸收系数谱.尽管此波段范围内的激光光子能量小于硅间接带隙,但当激光辐照在硅基光电二极管受光面时,在二极管两电极端仍然探测到了显著的脉冲光伏信号.光伏信号峰值强度与入射光强呈二次幂函数关系,表明其是双光子吸收过程.采用pn结等效结电容充放电模型,将光伏响应信号峰值与入射光强相关联,从中提取出硅的间接跃迁双光子吸收系数,改变入射波长得到系数谱.研究表明:     

Non-additivity of Methyl Group in the Single-electron Lithium Bond of H3C…… Li-H Complex

在B3LYP/6-311++G**及UMP2/6-311++G**水平上对单电子锂键复合物H₃C……Li-H的甲基非加和性进行了理论研究. 通过对复合物构型、能量、电荷转移及拓扑参数进行分析的基础上,讨论H₃C……LiH、H₃CH₂C……LiH、(H₃C)₂HC……LiH及(H₃C)₃C……LiH的作用强度. 结果表明,(H₃C)₃C自由基与LiH间形成的单电子锂键复合物的强度最强,其次为(H₃C)₂HC和H₃CH₂C,而H₃C自由基与LiH间形成的复合物的强度最弱,甲基非加和性使得体系的作用强度增强,这     

二溴卡宾与CH3OH多通道反应的理论计算

对单、三重态CBr2与CH3OH的多通道反应进行了理论计算. 在b3lyp/6-311g*水平上优化了势能面上构型并进行了构型确认. 计算了各物种经零点能校正的CCSD(T)能量. 结果表明, 单重态CBr2既可以与O－H键插入生成1,1-二溴代甲醚P1 (CH3OCHBr2), 也可以与C－H键插入生成2, 2-二溴代乙醇P3(Br2HCCH2OH). 同时, 存在单重态CBr2与CH3OH抽提双氢生成Pabs(CH2O+CH2Br2)的反应. 采用统计热力学及Wigner校正的Erying理论研究了主反应通道的热力学及动力学性质, 并对反应通道上的关键点进行了NBO和AIM分析.     

中波HgCdTe双色红外探测器优化模拟计算

针对光伏型中波HgCdTe双色红外探测器作了优化模拟计算，器件采用典型n-p-p-p-n结构和同时工作模式，建立的二维模型考虑了辐射复合、俄歇复合和Shockley-Read-Hall(SRH)复合三种复合机理，以及深能级辅助隧穿和带间直接隧穿效应，载流子穿过阻挡层势垒的隧道效应采用传递矩阵法计算.分析了双色器件光谱响应随吸收区SRH复合少子(电子)寿命的变化关系，以及串音与阻挡层组分的关系.模拟结果显示，随吸收区少子寿命变短，量子效率迅速下降；为了使器件有较高的量子效率，HgCdTe材料的SRH复合电子寿命应该至少在10ns以上.随阻挡层组分增大，势垒增高，串音迅速减小，大约在阻挡层组分差为0.03时下降到光学串音决定的稳定值，得出了抑制电学串音，阻挡层组分差的临界值为0.03. 关键词： HgCdTe中波双色红外探测器 光谱响应 光谱串音 少子寿命     

二维碳纳米薄膜制备的新途径——由自组装膜到石墨烯

本文描述了芳香族分子作为自组装单分子膜(SAMs)前驱体在电子辐照下引发芳香基团交联,在真空或惰性气氛中转化为具有较高热稳定性的碳纳米薄膜(CNMs)。CNMs具有足够的机械强度,可从其基底表面转移作为独立的薄膜材料,经高温淬火后转化为石墨烯。根据制备条件,如芳香分子前驱体的化学结构、电子辐照和淬火参数等,可以调整所制得的石墨烯的形状、结晶度、厚度、孔径等各种性能。各种芳香族硫醇,如低环及多环芳烃碳氢化合物,获得的CNMs的结构和功能由其单分子膜的结构所决定。本文详细讨论了电子辐射诱导SAMs芳香分子交联反应的机理。CNMs/石墨烯异质结构的非破坏性化学功能化组装为CNMs/石墨烯在电子、光子器件以及生物膜中的应用开辟了一条灵活的途径。     

TD-DFT Study on the Electronic Spectrum Properties of 2,7′-(Ethylene)-bis-8-hydroxyquinoline and Its Derivatives

The structures of 2,7′-(ethylene)-bis-8-hydroxyquinoline and its derivatives were optimized at the ground states using ab initio HF and B3LYP methods. At the same time, the molecular structures of the first singlet excited state for 2,7′-(ethylene)-bis-8-hydroxyquinoline and its derivatives were optimized by CIS/6-31G(d). The absorption and emission spectra based on the above structures were obtained by the time-dependent density functional theory (TD-DFT) by the B3LYP method with the 6-31G(d) basis set. The calculated results of luminescence originate from the electronic transition from the hydroxphenol ring of 8-hydroxyquinoline A to the pyridine ring of 8-hydroxyquinoline B. Their luminescence wave bands can be tuned by different substituents on the ligand of 8-hydroxyquinoline.     

PbTiO3铁电相及顺电相的声子色散理论计算

用统一的、参数物理意义明确的刚性离子模型研究了铁电体PbTiO₃铁电相和顺电相的声子色散关系和布里渊区中心有关相变的振动模,用比以往计算少得多的参数得到了比较好的结果,并提出了研究软模的简化模型构想. 关键词： 3')" href="#">PbTiO₃ 刚性离子模型 Born-Mayer势 声子色散