ClONO2异构化反应和分解反应的理论研究

用B3LYP/6 31+G(d)和MP2 (Full) /6 31+G(d)优化ClONO2 及其分解反应和异构化反应的过渡态和产物的分子结构 .在B3LYP/6 31+G(d)水平上计算了相关分子的振动频率 .ClONO2 的几何结构、振动频率和红外强度与实验测量值符合得很好 .找到了未曾报道的立体异构体 .对这一立体异构体进行了高级别理论方法CCSD(T) /6 311G(d)和QCISD(T) /6 311G(d)的几何结构优化和振动频率计算 ,表明它是一个稳定的立体异构体 .在所研究的几种反应中 ,ClONO2 分解为NO2 +ClO是最容易进行的反应 .而ClONO2 异构为立体异构体的反应是最难进行的反应 .其所需克服的过渡态的能垒为 4 81.5 2kJ/mol,而反应吸收能量为 2 99.85kJ/mol.次难进行的是ClONO2 经TS1到反应中间体M1,再经TS12而分解为ClNO +O2 的反应 .这个反应通道所需克服过渡态的能垒为 4 2 1.5 5kJ/mol,反应吸收能量为 15 7.98kJ/mol.从以上分析可知 ,和ClO +NO2 反应生成ClONO2 比较 ,ClONO2 具有较好的稳定性 .     

四苯基卟啉及其金属配合物在溴化银胶体上的表面增强喇曼光谱研究

研究了四苯基卟啉（H2TPP）及其金属配合物（AgTPP和MgTPP）在AgBr胶体上的表面增强喇曼光谱（SERS）。SERS光谱表明,吸附在ArBr胶体粒子表面的MgTPP和H2TPP分子分别发生银离子交换和银配位反应生成AgTPP,这种表面反应可能与激光照射有关。AgTPP分子在胶体粒表面的吸附导致卟啉大环的非平面化,使v8振动（M－N键伸缩振动）向高波数方向移动近10cm^-1。632.8nm激发下的表面喇曼谱以化学增强为主,而488.0nm激发下表面喇曼谱除化学增强效应外,还存在共振增强效应。     

Resonance Raman Study of Aggregated Meso-tetra(4-pyridinium) porphyrin Diacid

研究了近激子吸收带激发下四-(4-吡啶基)卟啉二酸(H₈TPyP⁶⁺)聚集体的共振拉曼光谱．测量了H₈TPyP⁶⁺单体和聚集体的紫外可见吸收谱和共振光散射光谱．在氘代位移的基础上结合相关体系振动光谱研究,对测得的H₈TPyP⁶⁺)单体和聚集体的拉曼谱带进行了指认．聚集体的形成导致H₈TPyP⁶⁺的卟啉环CC/CN面内伸缩振动向低波数方向位移2～6 cm^-1,而卟啉环鞍形面外振动带向高波数方向位移12cm^-1．基于拉曼谱带的强度和频率变化分析了聚集引起的H₈TPyP⁶⁺分子内结构变化和分子间氢键作用     

硝基甲烷异构化反应势能面的ab initio研究

在B3LYP/ 6 311++G(2d ,2p)水平上 ,优化得到硝基甲烷CH3 NO2 的 10种异构体和 2 3个异构化反应过渡态 ,并用G2MP2方法进行了单点能计算 .根据计算得到的G2MP2相对能量 ,探讨了CH3 NO2 势能面上异构化反应的微观机理 .研究表明 ,反应初始阶段的CH3 NO2 异构化过程具有较高的能垒 ,其中CH3 NO2 的两个主要异构化反应通道 ,即CH3 NO2 →CH3 ONO和CH3 NO2 →CH2 N(O)OH的活化能分别为 2 70 .3和 2 6 7.8kJ/mol,均高于CH3 NO2的C -N键离解能 .因而 ,从动力学角度考虑 ,CH3 NO2 的异构化反应较为不利 .     

Bichromatic Coherent Population Trapping Under Hanle Configuration

We report the observation of bichromatic coherent population trapping under the transition ^87 RbFg = 1 → Fc = 0 with two linearly polarized laser beams by means of a Hanle effect configuration. The mechanism behind this effect is identified, and numerical solutions for the pump rates equations are presented.     

Phase Transition and High Piezoactivity of Sb Doped （Na0.53K0.435Li0.035）Nb0.94Ta0.06 O3 Lead-Free Ceramics

Lead-free piezoelectric ceramics with the composition of （Na0.53K0.435Li0.035）Nb0.94Ta0.06 O3 （NKLNST） axe synthesized by a conventional solid-state sintering process. An MPB-like region between orthorhombic and pseudocubic phases is found in this system. The density, piezoelectric and dielectric properties axe enhanced greatly in this region. A composition （Na0.53K0.435Li0.035）（Nb0.94Ta0.06）O3 is found to have excellent electrical properties： d33 = 320pC/N, kp= 49% and kt =43%, as well as relatively low loss, tan δ=4.2%, and high relative density higher than 96%, which indicate that this ceramics is a promising lead-free piezoceramics replacing for lead zirconate titanate.     

光指针式微小位移测量仪

光指针式微小位移测量仪巧用光路将微小的位移量放大,从光指针终端的标度盘上可以直接读取实际的位移数值.     

两种气液两相流模型的应用和比较

本文应用MUSIG模型[1]和均一直径模型对某溶液堆台架模型堆芯内气液流动传热进行了数值模拟.在MUSIG模型中堆芯内离散相气泡被分为5组不同直径的气泡,用于分析堆芯内气泡的流动变化和大小分布,采用Luo and Svendsen[2]和Prince and Blanch[3]模型描述不同直径气泡组间的破裂和聚合.在均一直径模型中,堆芯内的气体被考虑为同一直径的组分,并且不考虑其破裂与聚合现象.计算得到采用两个模型的模拟结果并且对其进行了对比研究.结果显示应用MUSIG模型的计算结果与台架实验结果吻合更好.     

Photoluminescence Property of Co3O4 Nanowires

Co3O4 nanowire arrays are fabricated by electrodeposition with following heat-treatment in atmosphere ambient. Photoluminescence is investigated at 295K. In the experiment, when increasing the excitation light wavelength from 260 nm to 360 nm, two kinds of emissions corresponding to the increasing excitation light wavelength are observed. One of them alters the excited emission position, another keeps its emission position. The distinct behaviour of excited emissions related to the increasing excitation wavelength indicates that the mechanism of them must be different. According to the experimental comparison and first-principle calculation, the two kinds of emissions are discussed.     

Light Irradiation through Small Particles and Its Applications for Surface Nanostructuring in Near Field

We investigate the light scattering through small particles and its applications in nanostructuring, such as nanobumping, nanopatterning and dry laser cleaning. The theoretical calculation based on Mie theory provides an exact solution for sphere cavity resonance and plasmon resonance, which are two mechanisms for dielectric and metallic particles assisted surface nanostructuring in near field. The experimental results indicate that nanobumps on glass surface and subwavelength holes array on silicon surface can be formed without cracks with the self-assembly of 1 μm silica particle mask under laser irradiation. It is also found that the scattering wave by 40 nm gold particles can propagate 200 times away in terms of particle radius as recorded by photoresist under the UV light irradiation. Meanwhile, dry laser cleaning of 40nm gold particle on silicon wafer is demonstrated at plasmonic resonance frequency. The total cleaning efficiency is estimated to be 80%.