O4对利用天顶散射光法测量大气组分含量的影响研究

通过实验证明是否考虑O₄的存在对利用天顶散射光测量大气组分含量的结果存在影响.介绍了天顶散射光的观测原理、实验仪器、测量方法、光谱处理以及浓度反演过程.用具体的实验数据说明考虑O₄在实验波段内的吸收能提高NO₂和O₃浓度反演结果的准确性.同时将观测得到的臭氧垂直柱密度与美国TOMS观测数据进行了对比. 关键词： 4')" href="#">O₄ 臭氧 天顶散射光 DOAS     

CaCu3Ti4O12 陶瓷介电模量响应特性的研究

由于CaCu₃Ti₄O₁₂巨介电常数陶瓷的低频区直流电导较大, 本文采用模量 M"-f频谱表征与分析了低频和高频的两个松弛极化过程. 研究认为, 这两个特征峰属于晶界区Schottky 势垒耗尽层边缘深陷阱的电子松弛过程, 其中高频松弛峰起源于晶粒本征缺陷的电子松弛过程, 而低频松弛峰则为与氧空位有关的松弛极化过程. 对于CaCu₃Ti₄O₁₂这类低频下具有高直流电导的陶瓷材料, 采用模量频谱能更有效地分析研究其损耗极化机理. 关键词： 3Ti₄O₁₂陶瓷')" href="#">CaCu₃Ti₄O₁₂陶瓷 模量 松弛过程 电导     

Theory studies of the local lattice distortions and the EPR parameters for Cu2+, Mn2+ and Fe3+ centres in ZnWO4

The local lattice distortions and the electron paramagnetic resonance (EPR) parameters (g factors, hyperfine structure constants and zero-field splittings) for Cu²⁺, Mn²⁺ and Fe³⁺ in ZnWO₄ are theoretically studied based on the perturbation calculations for rhombically elongated octahedral 3d⁹ and 3d⁵ complexes. The impurity centres on Zn²⁺ sites undergo the local elongations of 0.01, 0.002 and 0.013 Å along the C₂ axis and the planar bond angle variations of 8.1°, 8.0° and 8.6° for Cu²⁺, Mn²⁺ and Fe³⁺, respectively, due to the Jahn–Teller effect and size and charge mismatch. In contrast to the host Zn²⁺ site with obvious axial elongation (～0.31 Å) and perpendicular (angular) rhombic distortion, all the impurity centres demonstrate more regular octahedral due to the above local lattice distortions. The copper centre exhibits significant Jahn–Teller reductions for the spin-orbit coupling and orbital angular momentum interactions, characterised by the Jahn–Teller reduction factor J (≈0.29 ? 1). The calculated EPR parameters agree well with the experimental results. The local structures of the impurity centres are analysed in view of the corresponding lattice distortions.     

Study of the d-f Emission,and f-d Ground-State and Excited-State Absorption of Nd3+ in Crystals Using the Simple Model

The simplified model for 4f-5d transitions is applied to obtain the line strengths for emission, ground-state absorption and excited states absorption involving 4f-5d transitions of Nd³⁺ in crystals. The results are host independent for the usual case where 5d crystal-field interaction can be considered as strong, in the sense that the calculated 5d-4f emission relative line strengths will be the same for Nd³⁺ in any host. Also the calculated 4f-5d absorption line strengths can be grouped by the 5d crystal-field components. For each 5d crystal-field component, the group of absorption line strengths for different 4f²5d transition final states forms a pattern independent of the 5d crystal-field component and the host. For practical cases, due to strong but still limited 5d crystal-field splitting, the transitions to different 5d crystal-field components may overlap each other. The theoretical results are used to interpret available experimental data.     

ZnAl2O4：Tb3+荧光粉的合成、结构及其光学性能研究

通过溶胶-凝胶法制备出不同Tb³⁺掺杂浓度和不同二次煅烧温度下的ZnAl₂O₄:Tb³⁺荧光粉, 并利用X射线衍射(XRD)和荧光光谱等对样品进行了表征。由XRD结果可知,当Tb³⁺掺杂的摩尔分数不大于9%,二次煅烧温度在600℃以上时,所得粉体为结晶性良好的尖晶石相。在紫外光激发下,ZnAl₂O₄:Tb³⁺荧光粉的发射光谱由位于488 nm(⁵D₄→⁷F₆)、542 nm(⁵D₄→⁷F₅)、587 nm(⁵D₄→⁷F₄ )和621.5 nm(⁵D₄→⁷F₃)的4个发射峰组成。研究发现,Tb³⁺的掺杂浓度和二次煅烧温度对样品发光强度有着重要影响,当Tb³⁺的摩尔分数为5%,二次煅烧温度为900℃时,ZnAl₂O₄:Tb³⁺荧光粉的发光最强,继续增加Tb³⁺掺杂浓度或提高煅烧温度,分别会出现浓度猝灭和温度猝灭现象。     

Prediction of Structure and Energy of Trans-1,4-Polybutadiene Glassy Surface by Atomistic Simulations of Free-Standing Ultrathin Films

Atomistic modeling of amorphous trans-1,4-polybutadiene (TPBD), using molecular mechanics and molecular dynamics (MD) simulations, is performed to generate three-dimensionally periodic bulk and two-dimensionally periodic thin film condensed phases. The condensed structures are constructed using multiple polymer chains. Structural and energetic relaxations and sampling of properties are performed using MD in the canonical ensemble (NVT) by a procedure that relieves local high-energy spots and brings the system to realistic thermodynamic states. The calculated surface energy for TPBD, 30.72 erg/cm², is in excellent agreement with the reported experimental value of 31 erg/cm². The structure of the surface layers is probed in terms of the atomic mass density variations, bond-bond orientation function profiles, and the distribution of the dihedral angles about the rotatable backbone bonds. The thickness of the surface layer over which the density varies smoothly but rapidly is found to be approximately 15 Å. The level of agreement of the calculated surface energy with the experimental value is superior in comparison to previous investigations in the literature using the atomistic approach for flexible polymers.     

Vibrational Spectroscopic Investigation and Theoretical Calculations of (E)-3-Phenyl-N-[4-(Phenyl-Amino) Quinazoline-7-yl] Acrylamide

ABSTRACT

Optimized geometrical structure and harmonic vibration frequencies of prior synthesized (E)-3-phenyl-N-[4-(phenyl-amino) quinazoline-7-yl] acrylamide were computed by ab initio HF and DFT/B3LYP methods using both 6-31G* and 6-311G** basis sets and the Moller–Plesset second-order perturbation (MP2) method merely at the 6-31G* level. The infrared (IR) spectrum of the title compound has been measured in the range of 400–4000 cm^?1. Complete vibrational assignments of the IR spectra were proposed. Moreover, the calculated wavenumbers of the title compound were compared with the experimental data. The correlation analyses indicate that good linearity relationships exist between the scaled theoretical vibration frequencies and the experimental values. Additionally, the atoms in molecules (AIM) method was applied to explore the possible intramolecular interactions in the title compound.     

Energy Transfer from the Upper Triplet States of Aromatic Molecules

The energy transfer from the upper triplet states of diphenylamine, naphthalene and triphenylene to toluene and hexene-1 is studed. Two mechanisms of dissipation transferred energy in solvents are discussed.     

Normal Coordinates Analysis for The M(NH3)2+ 4 Complex Ions in D4h and Td Symmetries. Simplified Molecular Models

A normal coordinates analysis for the M(NH₃)²⁺ ₄ complex ions in T_d symmetry (M = Zn, Cd, Co) and in D_4h symmetry (M = Cu, Pd, Pt) has been undertaken on the basis of a General Valence Force Field (GVFF), using simplified molecular models. Throughout the course of the present work, we have relaxed the point mass approximation for the NH₃-ligands in order to investigate, on a quantitative basis, some relevant ligand - framework coupling vibrations. The simplest molecular model able to accomplish this purpose is to treat the ammino group, in a linear ligator approximation. We show that these model calculations provide a satisfactory set of vibrational frequencies as well as consistent sets of force constants.