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 .     

电源最大输出功率的条件及公式的应用

当外电路的电阻等于电源内电阻时,电源输出功率最大,应用这个结论,可以省去许多计算步骤.但实际应用时还要注意一些问题,下面从几个方面加以讨论.1 电源实际输出功率与最大输出功率的区别 这是两个不同的概念,一些学生往往会用Pm=(?)/4r计算电源输出最大功率,其实,(?)/4r只是电源输出功率的极限,电源一般不在该状态下工作.     

Synthesis and luminescence properties of lanthanide(III) chelates with polyacid derivatives of thienyl-substituted terpyridine analogues

Two new polyacid derivative ligands of thienyl-substituted terpyridine analogues, N,N,N¹,N¹-[4′-(2?-thienyl)-2,2′:6′,2″-terpyridine-6,6″-diyl]bis(methylenenitrilo) tetrakis(acetic acid) (TTTA) and N,N,N¹,N¹-[2,6-bis(3′-aminomethyl-1′-pyrazolyl)-4-(2″-thienyl)pyridine] tetrakis(acetic acid) (BTTA), were synthesized, and the luminescence properties of their Eu³⁺ and Tb³⁺ chelates were investigated. The Eu³⁺chelates of the two ligands are strongly luminescent having luminescence quantum yields of 0.150 (TTTA-Eu³⁺) and 0.114 (BTTA-Eu³⁺), and lifetimes of 1.284 ms (TTTA-Eu³⁺) and 1.352 ms (BTTA-Eu³⁺), whereas their Tb³⁺ chelates are weakly luminescent. The TTTA-Eu³⁺ chelate was used for streptavidin (SA) labeling, and the labeled SA was used for time-resolved fluoroimmunoassay of insulin in human sera. The method gives the detection limits of 33 pg ml⁻¹.     

Nonlinear rheological behavior of silica filled solution‐polymerized styrene butadiene rubber

The reinforcement and nonlinear viscoelastic behavior have been investigated for silica (SiO₂) filled solution‐polymerized styrene butadiene rubber (SSBR). Experimental results reveal that the nonlinear viscoelastic behavior of the filled rubber is similar to that of unfilled SSBR, which is inconsistent with the general concept that this characteristic comes from the breakdown and reformation of the filler network. It is interesting that the curves of either dynamic storage modulus (G′) or loss tangent (tan δ) versus strain amplitude (γ) for the filled rubber can be superposed, respectively, on those for the unfilled one, suggesting that the primary mechanism for the Payne effect is mainly involved in the nature of the entanglement network in rubbery matrix. It is believed there exists a cooperation between the breakdown and reformation of the filler network and the molecular disentanglement, resulting in enhancing the Payne effect and improving the mechanical hysteresis at high strain amplitudes. Moreover, the vertical and the horizontal shift factors for constructing the master curves could be well understood on the basis of the reinforcement factor f(φ) and the strain amplification factor A(φ), respectively. The surface modification of SiO₂ causes a decrease in f(φ), which is ascribed to weakeness of the filler–filler interaction and improvement of the filler dispersion. However, the surface nature of SiO₂ hardly affects A(φ). © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2594‐2602, 2007     

三层同轴液柱内的热毛细对流的近似解析解

1引言在微重力下用浮区法生长高质量、大体积单晶体是一种很有应用前景的方法，但热毛细对流所引起的诸如宏观不均匀性、生长条纹等缺陷严重限制了这一方法的应用。目前，人们试着用液封方法抑制热毛细对流。文献［1～3］分别对两层流体系统内的热毛细对流所作的研究表明：通过液封，被封层内的热毛细对流可以得到显著抑制。本文对圆柱三层流体系统内的热毛细对流进行研究，为热毛细对流规律的揭示以及进一步总结出其控制方法提供了理论数值依据。2控制方程和边界条件考虑长为L的互不溶混的三层轴对称同轴液柱，如图1所示，两端壁保持定温T…     

Quantum Key Distribution Using High-Dimensional Quantum Error-Avoiding Code

Using high-dimensional quantum error-avoiding code, we present two new quantum key distribution protocols over a collective noisy channel, i.e. six-photon and five-photon quantum error-avoiding codes. Compared with the previous protocols using four-photon and three-photon quantum error-avoiding code, the qubit efficiencies of the new protocols have increases of 16.67% and 5% respectively. In addition, the security of these protocols is analysed with a conclusion that the new protocols are much more secure than the four-photon and three-photon ones.     

源气体对沉积的a-C∶F∶H薄膜结构的影响

采用微波电子回旋共振等离子体化学气相沉积(MWPECRCVD)方法,使用不同的源气体(CHF3CH4,CHF3C2H2,CHF3C6H6)体系制备了aC∶F∶H薄膜.由于CH4,C2H2,C6H6气体在等离子体中的分解反应不同导致了薄膜的沉积速率和结构上的差异.红外吸收谱的结果表明,用C6H6CHF3作为源气体沉积的薄膜中几乎不含H,而用C2H2CHF3所沉积的薄膜中的含氟量最高,其相应的CF振动峰位向高频方向偏移.薄膜的真空退火结果表明,aC∶F∶H薄膜的热稳定性除了取决于薄膜的CC键浓度外,还与CC键 关键词： 氟化非晶碳膜 电子回旋共振化学气相沉积 红外吸收光谱     

Development and applications of an on-line thermal neutron prompt-gamma element analysis system

This paper introduces the principles, instrumentation, implementation, and industrial applications of an on-line thermal neutron prompt-gamma element analysis system (using a²⁵²Cf neutron source, Am–Be neutron source, or neutron generator). The energy resolution of the system at the H prompt-gamma full-energy photopeak (2.22325 MeV) is 3.6 keV. The concentration measurement error of Al₂O₃, FeO₃, CaO, and SiO₂ is ±0.3%, ±0.1%, ±0.4%, and ±0.4%, respectively. The system has been tested on-site at both the Shandong and the Zhengzhou Aluminium Works. Our preliminary on-site measurements confirm that the stability, reliability, measurement range, and accuracy of the system can meet the requirements of the aluminium production process. Facilitation of this measurement at aluminium plants is expected to reduce plant costs by over 3 million dollars annually through reduced energy consumption, more rapid qualification of pulps being mixed during the production process, and in reduced labor costs.Other participants of Shandong and Zhenghou Aluminium Works are: Wang Aili, Zengshen, Dei Jianguo and Lu Jinnan, Wang Deyu, Jin Hequan.