CH3与NO2的反应

用时间分辨傅立叶红外光谱法和量子化学计算，研究了CH3自由基与NO2的基元反应．由248 nm激光光解CH3Br或CH3I得到CH3自由基．首次观测到了振动激发的产物OH、HNO和CO2．另一产物NO也被证实．由此确定了反应通道CH3O+NO，CH2NO+OH 和HNO+H2CO．其中CH3O+NO是主要的反应通道．还用CCSD(T)/6-311++G(df,p)//MP2/6-311G(d,p)的方法对上述通道的机理在理论上做了研究．理论计算的结果与实验观察相符．     

CH3CH2+O(3P)反应机理的理论研究

利用abinitio方法对CH3CH2+O(3P)反应进行了理论研究,在MP2/6311+G(d,p)水平上优化得到了反应途径上的反应物、中间体、过渡态和产物的几何构型和谐振频率,并在QCISD(T)/6311+G(d,p)水平上进行单点能计算.计算结果表明:CH2O+CH3、CH3CHO+H和CH2CH2+OH是主要反应产物,其中CH2O+CH3主要来自反应通道A1:(R)→IM1→TS3→(A),CH3CHO+H主要来自反应通道B1:(R)→IM1→TS4→(B),CH2CH2+OH主要来自直接抽提反应通道C1和C2:(R)→TS1(TS2)→(C).计算结果同时表明该反应生成CO的通道能垒是非常高的,CO应该不是主要产物.     

CH3CH2+N(4S)反应机理的理论研究

利用abinitio方法对CH3CH2+N(4S)反应进行了理论研究,在MP2/6-311+G(d,p)水平上优化得到了反应途径上的反应物、中间体、过渡态和产物的几何构型和谐振频率,并在QCISD(T)/6-311+G(d,p)水平上进行单点能计算.计算结果表明,CH2CH2+3NH和H2CN+CH3是此反应主要产物,CH3CHN+H是此反应次要产物.产物CH2CH2+3NH主要来自直接氢抽提反应通道,H2CN+CH3来自加成-解离反应通道,CH3CHN+H来自加成-解离反应通道.     

CH(X~2∏)+N_2O的反应机理研究

在G2 (B3LYP/MP2 /CC)理论水平上研究了CH(X2 ∏ )自由基与氧化二氮 (NNO)分子的反应 .计算了反应体系的最低二重态势能面上各驻点的构型参数、振动频率和能量 ,揭示了此反应存在两种机理和六个通道 .其中HC和NNO复合 ,生成中间体HC(N)NO ,解离得到产物HCN +NO ,这是最主要的通道之一 ;HC插入NO键 ,克服 38.9kJ/mol的势垒 ,产生富能的中间体HC(O)NN ,预测了五个反应通道 ,其中主要反应通道为 :NN +HCO .     

N(4S)+CH3X(X=Cl、Br)反应机理的理论研究

利用abinitio方法对N(4S)+CH3X(X=Cl、Br)反应进行了理论研究,在MP2/6311+G(d,p)水平上优化得到了反应途径上的反应物、过渡态和产物的几何构型和谐振频率,在MP2/6311++G(3df,2p)和QCISD(T)/6311+G(d,p)水平上进行单点能计算,并用G2MP2方法计算了所有物种的能量.计算结果表明,反应存在三条反应通道:H抽提反应通道a、Cl或Br抽提反应通道b和替代反应通道c.对于N(4S)+CH3Cl反应,a反应通道是主反应通道,b和c反应通道在反应中有少量贡献.对于N(4S)+CH3Br反应,a反应通道是主反应通道,b和c反应通道在反应中有一定的贡献.     

CH(X2∏)+N2O的反应机理研究

在G2(B3LYP/MP2/CC)理论水平上研究了CH(X^2Ⅱ)自由基与氧化二氮（NNO）分子的反应。计算了反应体系的最低二重态势能面上各驻点的构型参数、振动频率和能量，揭示了此反应存在的两种机理和六个通道。基中HC和NNO复合，生成中间体HC(N)NO，解离得到产物HCN+NO，这是最主要的通道之一；HC插入NO键，克服38.9kJ/mol的势垒，产生富能的中间体HC(O)NN，预测了五个反应通道，其中主要反应通道为：NN+HCO.     

Theoretical Study of Reaction Mechanism of 1-Propenyl Radical with NO

使用Gaussian 98程序包、在B3LYP/6-311++G**基组水平上对各物种进行全优化的基础上,用振动模式分析对1-丙烯基和NO反应的机理进行了充分阐明. 该反应体系共有7个反应通道和5组小分子最终产物,CH2O+CH3CN、CH2CHCN+H2O、CH3CHO+HCN、CH3CHO+HNC以及CH3CCH+HNO. 研究表明,反应通道C3H5￠+NO→IM1→TS1→IM2→TS2→IM3→TS3→CH3CHO+HCN在能量上是最为可行的.     

CH3CH2O及CH3CHOH与HO2反应机理的理论研究

采用CCSD(T)/cc-pVTZ//B3LYP/6-311++G(2df,2p)水平上对CH3CHOH + HO2和CH3CH2O + HO2反应体系的单、三重态反应机理进行了详细的理论研究.计算结果表明,CH3CHOH + HO2反应主要发生在单重态势能面上,其中四条通道均为快速自发过程;CH3CH2O + HO2反应在三重态势能面上的通道CH3CH2O + HO2 → 3IM11 → 3TS11 → P11 (CH3CH2OH + 3O2)为动力学和热力学的优势路径. 大气中CH3CHOH比CH3CH2O更容易稳定存在.     

CH3CH2O及CH3CHOH与HO2反应机理的理论研究

采用CCSD(T)/cc-pVTZ//B3LYP/6-311++G(2df,2p)水平上对CH3CHOH + HO2和CH3CH2O + HO2反应体系的单、三重态反应机理进行了详细的理论研究.计算结果表明,CH3CHOH + HO2反应主要发生在单重态势能面上,其中四条通道均为快速自发过程;CH3CH2O + HO2反应在三重态势能面上的通道CH3CH2O + HO2 → 3IM11 → 3TS11 → P11 (CH3CH2OH + 3O2)为动力学和热力学的优势路径. 大气中CH3CHOH比CH3CH2O更容易稳定存在.     

CH3NO2和CH3ONO结构及互异化反应的理论研究

采用了B3LYP、MP2方法,详细地计算了硝基甲烷(CH3ONO)和亚硝基甲酯(CH3NO2)的稳定结构、能量和振动频率等,并分析了它们的相对稳定性和相互转换的机理.结构优化结果表明,CH3ONO有两种稳定的构象cis和trans,CH3NO2有一种稳定的结构.在B3LYP/6-31G(d,p)方法的基础上,作出了CH3ONO的能量随CH3O-NO单键旋转的变化曲线图,定性地讨论了CH3ONO可能存在的稳定构象以及两种稳定构象之间互异化的机理.研究了CH3NO2与CH3ONO之间互异化的反应机理,计算了该异化反应发生时几何结构的变化以及最小能量途径,确定了该互异化反应实际上是C-N键和C-O键的断裂或形成的一个过程.     

Guided-Wave Two-Dimensional Acousto-Optic Scanner Using Proton-Exchanged Lithium Niobate Waveguide

Two-dimensional scanning of a 0.6328 mum guided-light beam has been realized using noncolinear acousto-optic (AO) coplanar Bragg diffraction together with colinear AO guided-mode to substrate radiation-mode conversion in a Z-cut Xpropagation LiNbO3 proton-exchanged (PE) waveguide. The two surface acoustic (SAW) waves utilized are at the center frequencies of 500 and 200 MHz, propagating in the Y and X axes, respectively. Two-dimensional scanning of approximately 720 resolvable light beam spots, namely, 18 40 (horizontal vertical) scanning, has been demonstrated using a light beam of 1.0 mm aperture. The total number of resolvable beam spots can be greatly increased from 720 by simply utilizing SAW transducers of larger bandwidth and a light beam of greater aperture. It should also be possible to significantly increase the diffraction efficiency from 3 % by optimizing the parameters of the PE waveguide and the SAWs.     

Femtosecond Transform-Limited Pulse Generation by Compensating for the Linear Chirp of SPM Spectra in Dispersion Shifted Fibers

A simple technique of pulse compression, based on the linear chirp compensation of self-phase modulation (SPM) spectra in dispersion shifted fibers, is demonstrated. The optimization procedure is carried out, for a short span of a single-mode fiber, using a parabolic law, which describes the behavior of the squared output pulse width versus the pump peak power in the case of Gaussian pulses. The experimental results give a minimum pulse duration of 233 fs, which is in good agreement with the model. Shorter and coherent pulses, down to 90 fs, have been obtained by inserting an interference filter at the optical output.     

Effect ofγ-radiation on the spectral luminescence characteristics of impure cadmium tungstate crystals

Results of a study of the effect of γ-radiation on the spectral luminescence properties of cadmium tungstate crystals doped with silver, bismuth, and molybdenum cations are presented. Spectral characteristics of the nondnnnoped crystals are briefly described. Absorption and photo and X-ray luminescence spectra of the crystals taken before and after exposure to γ-radiation (5.5·10⁴ Gy) are compared. It is found that the spectral characteristics of the crystals doped with silver, bismuth, and molybdenum cations do not change markedly after the exposure. The relation between the type of impurity-induced defects, individual characteristics of the impurity cations, and the character of the effect of γ-radiation on the spectral luminescence properties of impure crystals is analyzed (preliminarily). Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 1, pp. 55–60, January–February, 1997.     

Theoretical analysis and simulation of conjugate heights for dual-conjugate AO system in lidar

A multi-conjugate adaptive optics （MCAO） can offer a possibility of widening field of view （FOV） characterized by the isoplanatic angle, and the choose of conjugate height becomes a basic problem for MCAO, which influences the size of iosplanatic angle. Considering the application of lidar, the isoplanatic angle＇s expressions of two deformable mirrors （DMs） MCAO for uplink and downlink are deduced. The effects of conjugate heights for dual-conjugate AO are thoughtfully discussed, and the isoplanatic angles are further analyzed. The results show that the isopanatic angle varies with the conjugate height and reaches the maximum as the conjugate height is at the optimal altitude. Moreover, the optimal conjugate height changes with the propagation distance.     

Quick single-photon detector with many avalanche photo diodes working on the time division

Due to the limit of response speed of the present single-photon detector, the code rate is still too low to come into practical use for the present quantum key distribution (QKD) system.A new idea is put up to design a quick single-photon detector.This quick single-photon detector is composed of a multi-port optic-fiber splitter and many avalanche photo diodes (APDs).Au of the ports with APDs work on the time division and cooperate with a logic discriminating and deciding unit driven by the clock signal.The operation frequency lies on the number N of ports, and can reach N times of the conventional single-photon detector.The single-photon prompt detection can come true for high repetition-rate pulses.The applying of this detector will largely raise the code rate of the QKD, and boost the commercial use.     

Sorting of bending magnets for the SSRF booster

The Shanghai Synchrotron Radiation Facility(SSRF)booster ring,a full energy injector for the storage ring,is deigned to accelerate the electron beam energy from 150MeV to 3.5GeV that demands high extraction efficiency at the extraction energy with low beam loss rate when electrons are ramping.Closed orbit distortion(COD)caused by bending magnet field uniformity errors which affects the machine performance harmfully could be effectively reduced by bending magnet location sorting.Considering the affections of random errors in measurement,both ideal sorting and realistic sorting are studied based on measured bending magnet field uniformity errors and one reasonable combination of bending magnets which can reduce the horizontal COD by a factor of 5is given as the final installation sequence of the booster bending magnets in this paper.     

Improvement of four-wave mixing-based wavelength conversion efficiency in dispersion shifted fiber by 40-GHz clock pumping

40-GHz clock modulated signal as a pump to improve the efficiency of four-wave mixing (FWM)-based wavelength conversion in a 26.5-km dispersion shifted fiber (DSF) is investigated. The experimental results demonstrate that the conjugated FWM component has higher intensity with the clock pumping than that with the continuous-wave (CW) light pumping. The improvement of FWM-based wavelength conversion efficiency is negligible when the pump power is less than Brillouin threshold. But when the pump power is greater than Brillouin threshold, the improvement becomes significant and increases with the increment of pump power. The improvement can increase up to 9 dB if pump power reaches 17 dBm.     

Characterization of PolyA and PolyC mismatches by Raman spectroscopy

A.C mismatches are studied by Raman spectral characterization of PolyA, PolyC, and their equimolar complex in solution of 0.14 mol/L Na ,pH7.0.Experimental results show that A·C mismatches occur to be A/B (mainly A) conformers, and unlike Watson-Crick base pairing, this kind of mismatches is stabilized by only one hydrogen bond involving cytosine N4H2 and adenine N7.The formation of A·C complex makes the base stacking interactions much stronger, and conformation of the backbone more ordered, which leads to obvious Raman hypochromic effect with some shifts in corresponding bands.