胸腺嘧啶低能量VUV光解离路径的实验和理论研究

利用同步辐射真空紫外光电离质谱和理论计算研究了胸腺嘧啶的光解离反应路径, 通过改变光子能量得到不同的质谱信号, 光子能量在12.0 eV时主要的碎片有m/z=98 (C₄H₆N₂₄O⁺)、97 (C₄H₅N₂O⁺)、84 (C₃H₄N₂O⁺或C<     

环戊酮光电离解离的实验和理论研究

本文介绍了真空紫外光电离质谱结合理论计算研究环戊酮单分子的光电离解离过程. 在9.0∽15.5 eV能量范围内,测量了环戊酮离子及其碎片离子的光电离效率曲线. 通过光电离效率曲线,将环戊酮分子的电离能确定为9.23±0.03 eV,并确认碎片离子为：C₅H₇O⁺,C₄H₅O⁺,C₄H₈⁺,C₃H₃O⁺,C₄H₆⁺,C₂H₄O⁺,C₃H₆⁺,C₃H₅⁺,C₃H₄⁺,C₃H₃⁺,C₂H₅⁺, C₂H₄⁺. 利用量子化学计算方法,在ωB97X-D/6-31+G(d,p)理论水平基础上,提出了C₅H₈O⁺的解离机制. 通过对环戊酮解离路径的分析,发现开环和氢迁移过程为环戊酮离子解离的主要路径.     

异亮氨酸的真空紫外光电离和光离解

利用同步辐射光电离质谱结合理论计算, 研究了异亮氨酸的真空紫外光诱导电离解离．在光子能量为13 eV的质谱中探测到了m/z=86、75、74、69、57、46、45、44、41、30、28、18的碎片离子．对于异亮氨酸的主要碎片离子为：C₅H₁₂N⁺ (m/z=86)、C₂H₅NO₄⁺ (m/z=75)、C₅H₉⁺ (m/z=69)、C₄H₉⁺(m/z=57)和CH₄N⁺(m/z=30)．由光电离效率曲线得到出现势分别为：8.84±0.07、9.25±0.06、10.20±0.12、9.25±0.10、11.05±0.07 eV．结合量化理论计算(B3LYP/6-31++G(d,p)),详细给出了它们可能的生成路径．这些解离通道包括简单的键断裂反应和涉及中间体、过渡态的反应,实验值和理论计算的离子出现能或势垒一致．     

甲基环己烷在9∽15.5 eV能量区的真空紫外光电离研究

利用具有同步辐射源的反射式飞行时间质谱仪，研究甲基环己烷的真空紫外光电离和光解离. 观测到母体离子C₇H₁₄⁺和碎片离子C₇H₁₃⁺，C₆H₁₁⁺，C₆H₁₀⁺，C₅H₁₀⁺，C₅H₉⁺，C₄H₈⁺，C₄H₇⁺和C₃H₅⁺的光电离效率曲线. 测定甲基环己烷的电离能为9.80±0.03 eV，通过光电离效率曲线确定其碎片离子的出现势. 在B3LYP/6-31G(d)水平上对过渡态、中间体和产物离子的优化结构进行表征，并使用G3B3方法计算其能量. 提出主要碎片离子的形成通道. 分子内氢迁移和碳开环是甲基环己烷裂解途径中最重要的过程.     

苯和苯胺在深紫外光照射下的电离和解离

本文利用自主研制的反射式飞行时间质谱仪结合177.3 nm深紫外激光研究了苯和苯胺分子的光电离与光解离过程. 质谱实验发现苯在177.3 nm皮秒激光作用下发生高效电离并观测到不对称C-C键解离形成的以C₄H₃⁺为主的较小碎片峰. 相比之下，苯胺的深紫外光电离中主要产生一个C₅H₆^+·离子自由基和一个较小丰度的C₆H₆^+·碎片，分别对应于CNH分子和NH自由基的去除. 结合第一性原理计算，诠释了苯和苯胺这两个仅有一个氨基差异的分子光解离路径，揭示苯和苯胺分子中氢原子转移对于C-C或C-N键断裂的关键重要作用.     

异戊二烯解离光电离理论研究

利用CBS-QB3理论计算方法研究了异戊二烯的可能解离通道.获得了主要碎片离子C₅H₇⁺,C₅H₅⁺,C₄H₅⁺,C₃H₆⁺,C₃H₅⁺,C₃H₄⁺,C₃H₃⁺的C₂H₃⁺的结构以及这些解离通道的解离能,并给出了相应的过渡态和中间体的结构和位垒.得到的异戊二烯电离势及主要碎片离子的出现势均与实验值符合的较好.最后,通过理论和实验结果的对比讨论了各通道的解离机理.     

卡培他滨、5''-脱氧-5-氟胞苷和5''-脱氧-5-氟尿苷的真空紫外光电 离、光解离

利用红外激光解吸/真空紫外光电离质谱方法, 研究了核苷类抗癌药物卡培他滨及其代谢物5'-脱氧-5-氟胞苷和5'-脱氧-5-氟尿苷的光电离、光解离过程. 较低光子能量下, 可在质谱图上观察到分子离子峰及少量碎片离子, 增加光子能量使碎片离子峰大量出现. 另外对三种核苷的特征碎片, 如(M- H₂O)⁺、(Base+H)⁺、(Base+2H)⁺、(Base+30)⁺、(Base+60)⁺及戊糖离子进行了归属,并对可能的解离路径进行了讨论. 利用量子化学从头算方法研究了三种核苷可能的脱羟基过程及相应能量.     

N2O+离子A2Σ+电子态高振动能级的转动结构分析

利用一束波长为36055nm的激光，通过(3+1)共振多光子电离方法制备纯净的且处于X²Π_1/2，3/2(000)态的N₂O⁺离子，用另一束激光激发所制备的离子到第一电子激发态A²Σ⁺的不同振动能级，然后解离，通过检测解离碎片NO⁺强度随光解光波长的变化，得到了转动分辨的N₂     

异补骨脂素热解实验和理论研究

利用同步辐射真空紫外光电离质谱技术,在不同光子能量下,研究了异补骨脂素(C₁₁H₆O₃)的低压热解,探测了不同温度下异补骨脂素的热解产物及其与前驱体的比例. 实验结果表明,异补骨脂素的主要热解产物是CO及其依次消去CO的产物(C₁₀H₆O₂和C₉H₆O). 利用密度泛函理论计算异补骨脂素的解离途径,并利用过渡态理论计算了竞争通道的反应速率常数. 通过实验和理论的结合,确定了异补骨脂素主要解离路径和相应产物的分子结构.     

邻碘甲苯分子光解动力学的飞秒时间分辨质谱研究

利用飞秒时间分辨质谱技术研究了邻碘甲苯分子在266 nm激发下的光解动力学. 光解产物碎片通过800 nm强激光场下的多光子电离实现探测. 拟合光解产物C₇H₇自由基和I原子随泵浦-探测延迟时间变化的信号,得到解离时间为38±50 fs,它反映的是266 nm同时激发nσ^*和ππ^*态后C-I键的平均解离时间. 此外,还利用基态碘原子的共振波长298.23 nm作为探测光,通过共振增强多光子电离方法对解离生成的基态碘原子进行了选择性探测. 拟合I⁺随泵浦-探测延迟时间变化的信号,得到解离时间为40±50 fs,这与通过800 nm多光子电离得到的解离时间一致,表明解离生成的主要产物是基态碘原子.     

白光和红绿蓝光LED可调光源研制

为了提高LED光源色温和亮度的调节精度和准确度,结合色温由低向高变化时光色所呈现的渐变特点,提出了一种低色温白光LED灯珠、高色温白光LED灯珠加红绿蓝光LED灯珠补偿式调光的方法.将色温分成三个部分进行调节,每个部分选用不同的LED灯珠组合来进行调光.实验结果表明:不同组合情况下的LED光源的初始输出色温相对于目标值的偏差范围在1％以内;亮度可以在保证色温不变的情况下独立进行调节,初始输出值与目标值的偏差范围在1％以内;经过微调之后可以达到目标值;达到了色温和亮度独立调节的要求;光源发光稳定,不会因为长时间工作而影响调节精度.     

Visualization and interferometry for cylindrical and spherical sample tomography and profilometry

A technique combining image processing and laser interferometry for visualizing and detecting the deformation of transparent cylindrical and spherical sample is proposed. This deformation includes geometric deformation such as volume transition in profilometry and physical deformation such as refractive index change in tomography. Phase contour lines are used for quantitative analysis and graphical representation of the deformation. This method allows us to visually detect the spatial variation of the deformation field and to evaluate the test quality such as misalignment of optical system. A theoretical analysis using phase contour map to characterize the deformation field is described in detail. A method using phase contour map to qualify the interferometric test is proposed. Analysis of test examples is carried out. Suggestions on using phase contour line method to ameliorate test system design are finally discussed.     

Quantum and Classical Disparity and Accord

Discrepancies and accords between quantum (QM) and classical mechanics (CM) related to expectation values and periods are generally found for both the harmonic oscillator (SHO) and a free particle in a box (FPB), which may apply generally. These indicate non-locality is expected throughout QM. The FPB energy states violate the Correspondence Principle. Previously unexpected accords are found and proven that 〈x ²〉 _CM =〈x ²〉 _QM and τ _CM =τ _QMb (beat period i.e. beats between the phases for adjoining energy states) for the SHO for all quantum numbers, n. However, for the FPB the beat periods differ at small n. It is shown that a particle’s velocity in an infinite square well varies, no matter how wide the box, nor how far the particle is from the walls. The quantum free particle variances share an indirect commonality with the Aharonov-Bohm and Aharonov-Casher effects in that there is a quantum action in the absence of a force. The concept of an “Expectation Value over a Partial Well Width” is introduced. This paper raises the question as to whether these inconsistencies are undetectable, or can be empirically ascertained. These inherent variances may need to be fixed, or nature is manifestly more non-classical than expected.     

黑克、布劳、及伯曼-温采尔代数的诱导及分导系数和量子经典李代数的耦合与重新耦合系数

本文总结了计算黑克、布劳、及伯曼 温采尔代数在各种工数链下诱导及分导系数的线性方程方法(LEM)。特别强调了关于A,B,C,D型李代数及其量子情形与其中心代数之间的舒尔 魏尔 布劳双关性关系。这一关系使我们能够利用相应中心代数的诱导及分导系数计算出经典李代数及其量子情形的耦合与重新耦合系数。讨论了从该方法得到B,C,D型李代数不可约表示克罗内克积分解的应用。基于LEM还得到了处理对应于置换群CG系列问题的黑克代数张量积的方法。     

Rapid and flexible laser marking and engraving of tilted and curved surfaces

We present a novel method for rapid and flexible laser marking and engraving of tilted, curved and freeform work-piece surfaces. The method is based on integrating a three-dimensional (3D) laser measurement system into a 3D laser marking system. We use the same laser source and optics for measurement and processing with a minimum of additional hardware components. A low power CW laser regime is used to measure the 3D shape of a work-piece surface while a high-peak power-pulsed laser regime is used for processing. The acquired 3D surface data are used to determine the 3D trajectory of the processing beam focus. Neither the 3D shape of the work-piece nor its orientation needs to be known in advance as long as the processed surface lies within the working range of the 3D laser processing system. This eliminates the need for exact work-piece positioning before processing and substantially improves processing flexibility (allowing, e.g. variations in work-piece shape or/and orientation from mark to mark). This paper discusses key issues concerning an implementation of the method and presents typical examples of markings and engravings, which demonstrate the advantages of the method with respect to the existing industrial 2D and 3D laser marking and engraving methods. The method can also be applied to flexible laser structuring and microprocessing of curved surfaces.     

国外超导材料技术研究政策和方向

超导材料技术是21世纪具有战略意义的高新技术,极具发展潜力和市场前景。世界各发达国家纷纷制定研发计划,给予高度重视和大力支持,加快超导材料技术的基础研究和产业化发展。主要从美国、日本、欧洲国家、韩国等国家的相关研发计划、政策以及主要科研机构的研发概况出发,阐明目前国外超导材料技术的研究政策和方向。     

Geometry and Elasticity of Strips and Flowers

We solve several problems that involve imposing metrics on surfaces. The problem of a strip with a linear metric gradient is formulated in terms of a Lagrangian similar to those used for spin systems. We are able to show that the low energy state of long strips is a twisted helical state like a telephone cord. We then extend the techniques used in this solution to two–dimensional sheets with more general metrics. We find evolution equations and show that when they are not singular, a surface is determined by knowledge of its metric, and the shape of the surface along one line. Finally, we provide numerical evidence by minimizing a suitable energy functional that once these evolution equations become singular, either the surface is not differentiable, or else the metric deviates from the target metric.     

Spectroscopy and Photophysics of Iso- and Alloxazines: Experimental and Theoretical Study

We present a systematic study of the effect of methyl substitution on iso- and alloxazines in acetonitrile solutions. Substitution patterns have profound effects on both spectral and photophysical properties, with fluorescence quantum yields varying by more than an order of magnitude. TD-DFT calculation were used for the first time to correlate electronic structure changes with the substitution patterns, with good agreement between calculated and theoretical band positions and oscillator strengths. Both n-pi* and pi-pi* states in these compounds are predicted, with the oscillator strengths indicating that only the pi-pi* states should be observable in the absorption spectra. Substitution patterns are shown to be responsible for energy order inversion between these states.     

Divergence- and Curl-Preserving Prolongation and Restriction Formulas

We present new second-order prolongation and restriction formulas which preserve the divergence and, in some cases, the curl of a discretized vector field. The formulas are suitable for adaptive and hierarchical mesh algorithms with a factor-of-2 linear resolution change. We examine both staggered and collocated discretizations for the vector field on two- and three-dimensional Cartesian grids. The new formulas can be used in combination with numerical schemes that require a divergence-free solution in some discrete sense, such as the constrained transport schemes of computational magnetohydrodynamics. We also obtain divergence-preserving interpolation functions which may be used for streamline or field line tracing.