7Li2(X1Σ+g)分子的振动能级、转动惯量及离心畸变常数

使用密度泛函理论B3LYP和B3P86，以及组态相互作用方法CCSD(T)和QCISD, 利用多个基组对⁷Li₂(X¹Σ⁺_g)分子的平衡核间距(R_e)、谐振频率(ω_e)和离解能(D_e)进行了计算, 发现在CCSD(T)/cc-PVQZ理论水平下得到的结果(R_{e相似文献}   

表面效应对Li掺杂的ZnO薄膜材料p型电导的影响

利用第一性原理的方法研究了在ZnO非极性表面和极性表面的不同原子层中, 分别用Li原子去替位Zn原子(记为Li_Zn)后的相对稳定性和热离化能. 计算结果表明Li_Zn处于ZnO表面区域时的稳定性优于在ZnO体中时的稳定性, 并且Li_Zn在表面区域的热离化能要比它在体结构中的热离化能大很多, 于是, ZnO表面效应的存在会使Li掺杂的ZnO薄膜材料的p型导电能力大幅度降低. 这个结果对低维ZnO体系p型掺杂有着重要的指导意义. 我们进一步发现, 在不同的ZnO表面区域里Li_Zn的热离化能会表现出很大的差异是源于不同的表面具有不同的静电势分布.     

纯Cr2O3包覆Li4Ti5O12微球的制备及其储锂性能研究

The pure Cr₂O₃ coated Li₄Ti₅O₁₂ microspheres were prepared by a facile and cheap solutionbased method with basic chromium(III) nitrate solution (pH=11.9). And their Li-storage properties were investigated as anode materials for lithium rechargeable batteries. The pure Cr₂O₃ works as an adhesive interface to strengthen the connections between Li₄Ti₅O₁₂ particles, providing more electric conduction channels, and reduce the inter-particle resistance. Moreover, LixCr₂O₃, formed by the lithiation of Cr₂O₃, can further stabilize Li₇Ti₅O₁₂ with high electric conductivity on the surface of particles. While in the acid chromium solution (pH=3.2) modification, besides Cr₂O₃, Li₂CrO₄ and TiO₂ phases were also found in the final product. Li₂CrO₄ is toxic and the presence of TiO₂ is not welcome to improve the electrochemical performance of Li₄Ti₅O₁₂ microspheres. The reversible capacity of 1% Cr₂O₃-coated sample with the basic chromium solution modification was 180 mAh/g at 0.1 C, and 134 mAh/g at 10 C. Moreover, it was even as high as 127 mAh/g at 5 C after 600 cycles. At-20℃, its reversible specific capacity was still as high as 118 mAh/g.     

Bi12GeO20晶体的位错蚀斑与对称群

用化学浸蚀法系统的研究了Bi₁₂GeO₂₀晶体{100},{100},{111}等晶面独特浸蚀斑规律并用对称群理论进行分析.理论预示的蚀斑形态与实验结果符合很好.显示位错蚀斑是由{112}晶面组成,即晶体的惯态面为{112}.     

GeO2-Bi2O3-MOx(MOx=WO3, BaO)玻璃近红外超宽带发光的研究

用高温熔融法制备了(99.5-χ) GeO₂-χBaO-0.5Bi₂O₃(χ=3, 6, 9mol%)与(99.5-φ)GeO₂-φWO₃-0.5Bi₂O₃(φ=3，6，9mol%)玻璃，测定了样品的发射光谱(800nmLD激发)、吸收光谱、荧光衰减和差热曲线.实验结果表明，在GeO₂-WO₃-Bi₂O₃系统玻璃中，随着WO₃含量的增加，在1260nm处的发光强度增强，荧光半高宽(FWHM)增宽，荧光寿命增长，而且玻璃的吸收边带发生明显的红移；在GeO₂-BaO-Bi₂O₃系统玻璃中，随着BaO含量的增加，玻璃在1290nm处发光强度增强，FWHM增宽，荧光寿命增长，吸收边带也有明显的红移.从吸收边带发生红移的情况，结合发射光谱和荧光衰减曲线特性，我们推断玻璃样品在近红外的宽带发光可能由Bi⁵⁺离子所引起.从荧光特性估算了玻璃的σ_p×τ和σ_p×Δλ值，这些玻璃均具有较小的σ_p×τ和较大的σ_p×Δλ特性，说明GeO₂-Bi₂O₃-MO_x(MO_x=WO₃, BaO) 系统玻璃是研制成近红外(O到S波段)超宽带光纤放大器的良好材料.     

Li2分子自旋一致激发态a3Σ+u和b3Πu的分析势能函数的从头算

使用对称性匹配簇-组态相互作用方法首次计算了Li₂分子自旋一致激发态a³Σ⁺_u和b³Π_u的离解能、平衡几何及其谐振频率。使用最小二乘法、利用Murrell-Sorbie函数形式拟合出了Li₂分子三重态的第一激发态a³Σ⁺_u 和第二激发态b³Π_u的完整势能函数，并计算了这两个态的光谱常数 (B_e, α_e, ω_e 和 ω_eχ_e) 和力常数 (f₂, f₃和f₄)。得到了Murrell-Sorbie函数形式既适用于基态、又适用于激发态的结论。将计算得到的激发态（a³Σ⁺_u和b³Π_u）的离解能、平衡几何及其谐振频率与实验结果及其它理论计算结果进行了比较。从比较的结果中可以清楚地看出，本文的计算结果在计算精度方面有很大的改进。     

Mg2(BH4)2(NH2)2脱氢机理的理论研究

对Mg₂(BH₄)₂(NH₂)₂的脱氢机理展开系统的理论研究发现相对于分子内的脱氢过程,分子间的脱氢过程在热力学和动力学方面都是比较有利的. Mg₂(BH₄)₂(NH₂)₂脱氢过程的第一步是BH₄^-中的B-H^δ-和NH2-中     

糠醇辅助的聚合凝胶法制备纳米Li4Ti5O12负极材料

以硝酸锂、钛酸正丁酯和糠醇为反应物,采用糠醇聚合凝胶法制备了纳米Li₄Ti₅O₁₂粉体．利用XRD、SEM和BET比表面测试对产物进行了表征,并研究了纳米Li₄Ti₅O₁₂粉体作为锂离子电池负极材料的电化学性能．在700℃或更高温度烧结时产物为纯相的尖晶石型．通过柠檬酸、聚乙烯吡咯烷酮、十六烷基三甲基溴化铵(CTAB)表面活性剂的加入能够减少产物颗粒的团聚程度,增大粉体的比表面积,提高其电化学性能．加入0.5 g CTAB、700℃烧结12 h的Li₄Ti₅O₁₂粉体展示出最高的比容量和最佳的循环性能,10 C下充电比容量高达156.7 mAh/g．     

π-(C5H5)2TiCl2·AlR3系可溶性催化剂的电子自旋共振波谱

本文稿研究了Al(iC₄H₉)₃、Al(C₂H₅)₃、Al(C₂H₅)₂Cl、Al(C₂H₅)Cl₂等与π-(C₅H₅)₂TiCl₂所形成的络合物在无溶剂以及在溶剂稀释过程中的电子自旋共振波谱。根据实验结果,作者认为未成对电子是定位在Al²⁷核一端,电子云可延伸到α氢原子位置上,并指出溶剂主要起着分散络合物的作用。     

新型光存储材料Sr2SnO4: Tb3+, Li+ 的合成及其红外上转换光激励发光性能的研究

采用高温固相法获得了一种只具有 微弱余辉的新型电子俘获型光存储材料Sr₂SnO₄:Tb^{3 +}, Li ⁺. 发光性能研究结果表明: 该材料对980 nm的红外激光具有很好的上转换光激励信息读出响应, 同时292 nm紫外光为其最佳信息写入光源. 光存储性能研究结果表明: 该材料的浅陷阱较少, 因此其余辉发光很弱, 不到500 s; 另一方面, 该材料中存在大量的深蓄能陷阱. 因此, Sr₂SnO₄: Tb^{3 +}, Li⁺是一种具有较好实际应用价值的新型电子俘获型光存储材料. 此外, 还讨论了Sr₂SnO₄: Tb^{3 +}, Li⁺的光存储发光机理.     

Li3VO4-Li4SiO4-Li4GeO4赝三元系相图的研究

本文用差热分析法和高温、室温X射线衍射法对Li₃VO₄,Li₄SiO₄的相变过程,Li₃VO₄-Li₄SiO₄,Li₃O₄-Li-4GeO₄赝二元系相图以及Li₃VO₄-Li₄SiO₄-Li₄GeO₄赝三元系相图室温截面进行了研究。发现在Li₃VO₄-Li₄SiO₄,Li₃VO₄-Li₄GeO₄赝二元系中,由于Li₄SiO₄或Li₄GeO₄的加入而使Li₃VO₄的高温γ_II相稳定存在于室温,从而得到一种新的具有高电导率的锂离子导体。作者认为探寻使高温态稳定存在于室温的方法是探索新的离子导体研究中有效途径之一。 关键词：     

Li4SiO4-Li3VO4赝二元系和Li4GeO4-Li4SiO4-Li3VO4赝三元系中新的锂离子导体

本文在室温到300℃的温度范围内研究了Li₄SiO₄-Li₃VO₄和Li₄GeO₄-Li₄SiO₄-Li₃VO₄体系中的离子导电性,发现γ_II相固溶体Li_3+xV_1-xSi_xO₄是好的锂离子导体。所研究的成分中Li_3.3V_0.7Si_0.3O₄的离子电导率最高,室温下为1×10^-5Ω^-1·cm^-1,在42—192℃的电导激活能为0.36eV,电子电导率可以忽略,因而这是迄今所发现的最好的锂离子导体之一。粗略确定了Li₄GeO₄-Li₄SiO₄-Li₃VO₄三元系中电导率高的范围,发现在Li_3.5V_0.5Ge_0.5O₄中Si部分取代Ge可以使电导率进一步提高,Li_3.5V_0.5Ge_0.4Si_0.1O₄的室温电导率可达1.3×10^-5Ω^-1·cm^-1,电导激活能为0.40eV。 关键词：     

Li+ ion conducting γ solid solutions in the systems Li4XO4-Li3YO4: X=Si,Ge, Ti; Y=P,As, V; Li4XO4-LiZO2: Z=Al,Ga, Cr and Li4GeO4-Li2CaGeO4

A wide variety of solid solutions with a structure related to that of γ Li₃PO₄ may be prepared. These include materials such as lisicon, Li_2+2xZn_1-xGeO₄ and the title systems, many of which have not been studied previously. Conductivity data are presented for eight systems: Li₄GeO₄-Li₃(P, As, V)O₄; Li₄TiO₄-Li₃(As, V)O₄; Li₄GeO₄-Li(Ga, Al)O₂; Li₄GeO₄-Li₂CaGeO₄ and the results compared with those reported in the literature for Li₄SiO₄-Li₃(P, As, V)O₄ systems and lisicon. dc polarisation measurements were made on four of the system and it was found that the electronic transference number is 10^?4 or less. The materials with the highest conductivity were found in the systems, Li₄ (Ge, Ti) O₄-Li₃ (As, V)O₄ with σ ~ (3 to 4) × 10^?5 Ω^?1 cm^?1 at room temperature. It is noted that the systems with the highest conductivity are generally those with the largest unit cell volume.     

磁控共溅射法制备的Zn2GeO4多晶薄膜结构及其光致发光研究

用射频磁控共溅射方法在不同温度的单晶硅基片上生长薄膜,然后在800℃真空环境下对薄膜进行退火处理,成功获得了结晶状态良好的Zn₂GeO₄多晶薄膜.利用X射线衍射(XRD),X射线光电子能谱(XPS)和原子力显微镜(AFM)对薄膜进行了结构、成分和形貌分析,研究了基片温度对三者的影响. 结果显示,当基片温度升高到400℃以上时,薄膜中的Zn₂GeO₄晶粒在(220)方向上显示出了明显的择优取向. 当基片温度在500—600℃范围内,有利于GeO₂结晶相的形成. XPS显示薄膜中存在着Zn₂GeO₄,GeO₂,GeO,ZnO四种化合态. 同时,随着基片温度的升高,晶粒尺寸增大且薄膜表面趋于平整. 薄膜的光致发光在绿光带存在中心波长为530和550nm两个峰,应该归因于主体材料Zn₂GeO₄中两个不同的Ge²⁺的发光中心. 关键词： 射频磁控溅射 2GeO₄')" href="#">Zn₂GeO₄ 荧光体     

Li3VO4-Li4TO4(T=Ge,Si)固溶体离子导体7Li的NMR研究

在150—573K温度范围内,研究了固溶体Li₃VO₄-Li₄TO₄(T=Ge,Si)系统不同成分的⁷Li的NMR谱。发现γ_II相固溶体室温⁷Li的NMR线宽和自旋晶格弛豫时间T₁的值都比Li₄GeO₄,Li₄SiO₄和Li₃VO₄小约一个数量级。这表明在γ_II相固溶体离子导体中,Li⁺离子运动有可能比固溶前有数量级增长。同时还发现⁷Li的电四极分裂伴线数随成分和温度而异,以及伴线强度百分比依赖于温度。这反映γ_II相的不同成分中,间隙Li⁺离子占有的不等价位置个数不同,而Li⁺离子在每个不等价位置上的占有率又随温度而变化。 关键词：     

Li2SO4—Li2B2O4,Li2SO4—(NH4)2SO4赝二元系相图及离子导电性研究

本文用差热分析和X射线衍射方法对Li₂SO₄-Li₂B₂O₄和Li₂SO₄-[NH₄]₂SO₄两个赝二元系相图进行了研究。Li₂SO₄-Li₂B₂O₄是共晶体系,共晶温度为720℃ 关键词：     

Yb and Yb-Eu luminescent properties of the Li2Lu5O4(BO3)3 phase

The luminescence of Yb³⁺ in the oxyborate Li₂Lu₅O₄(BO₃)₃ is reported. At low temperature, in addition to the usual ytterbium infrared emission, this phosphor presents an emission in the ultraviolet () which corresponds to the transition from the charge transfer state (O-Yb) to the 4f levels of Yb³⁺. The temperature quenching Tq50% is equal to 120 K. The infrared emission studied at room temperature is located between 950 and 1100 nm.Europium emission quenching in the Li₂Yb₅O₄(BO₃)₃ phase is related to Eu→Yb transfer by cross-relaxation. The reverse Yb→Eu transfer by cooperative sensitization is highlighted in the codoped Li₂Lu₅O₄(BO₃)₃ compound.     

The electronic structure and photoluminescence properties of Ca2GeO4:Eu in ultraviolet and vacuum ultraviolet region

Ca₂GeO₄:Eu³⁺ phosphors were synthesized by the solid state method. The ultraviolet and vacuum ultraviolet excited photoluminescence properties were investigated in detail. It revealed that the emission of Ca₂GeO₄:Eu³⁺ comprised two parts: the red emission of Eu³⁺ and host defect emission in 330-550 nm. Ca₂GeO₄:Eu³⁺ presented intense excitation intensity at 163-200 and 466 nm, which suggested the potential applications in plasma display panels and light emitting diodes. The excitation spectra were studied to identify the photoluminescence mechanisms of Ca₂GeO₄:Eu³⁺. First principles calculation within the local density approximation of the density functional theory was applied to calculate the electronic structure and linear optical properties of Ca₂GeO₄.     

Temperature-dependent far-infrared properties of Bi12GeO20 single crystal

Far-infrared reflectivity spectra of bismuth germanium oxide (Bi12GeO20) single crystals are measured from room temperature down to 10 K. All the reflectivity spectra are fitted to a complex dielectric function ε(ω) in the factorised form. Phonon modes at low frequency are found to develop upon decreasing temperature and gain considerable spectrum weight below 150 K. The temperature-dependent static dielectric constants are obtained from the Lyddane-Sachs-Teller relation based on the obtained oscillator parameters. The dielectric constants are found to increase upon decreasing temperature, which is attributed to the charge transfer among the ions in the unit cell with the temperature varying.