Ammonolysis of morpholine‐2,5‐diones: participation of the primary amide group. Part 2

The ammonolysis of three morpholine‐2,5‐dione derivatives was investigated and the mechanism ascertained by kinetic studies and theoretical calculations. The kinetics, followed by high‐performance liquid chromatography analysis, evidenced the presence of two intermediates, which were isolated and characterized. The ammonolysis occurs with a complex mechanism involving two consecutive reactions followed by two parallel ones. The second step of the whole reaction involves an anchimeric assistance of the primary amide group. The pseudo‐first‐order rate constants were calculated by appropriate equations, which describe the single steps of the process. Computational density functional theory investigations of vicinal primary amide group participation were performed using a model compound, and the transition states were generated. The theoretical calculations evidenced the essential role exerted by ammonia, which acts as a proton transfer. Copyright © 2011 John Wiley & Sons, Ltd.     

Theoretical study of neighboring carbonyl group participation in the elimination kinetics of chloroketones in the gas phase

The gas‐phase elimination of kinetics 4‐chlorobutan‐2‐one, 5‐chloropentan‐2‐one, and 4‐chloro‐1‐phenylbutan‐1‐one has been studied using electronic structure methods: B3LYP/6‐31G(d,p), B3LYP/6‐31++G(d,p), MPW91PW91/6‐31G(d,p), MPW91PW91/6‐31++G(d,p), PBEPBE/6‐31G(d,p), PBEPBE /6‐31++G(d,p), and MP2/6‐31++G(d,p). The above‐mentioned substrates produce hydrogen chloride and the corresponding unsaturated ketone. Calculation results of 4‐chlorobutan‐2‐one suggest a non‐synchronous four‐membered cyclic transition state (TS) type of mechanism. However, in the case of 5‐chloropentan‐2‐one and 4‐chloro‐1‐phenylbutan‐1‐one, the carbonyl group assists anchimerically through a polar five‐membered cyclic TS mechanism. The polarization of the C? Cl bond, in the sense of C^δ+…Cl^δ?, is a rate‐determining step in these elimination reactions. The significant increase in rates in the elimination of 5‐chloropentan‐2‐one and 4‐chloro‐1‐phenylbutan‐1‐one is attributed to neighboring group participation due to the oxygen of the carbonyl group assisting the C? Cl bond polarization in the TS. Copyright © 2010 John Wiley & Sons, Ltd.     

Numerical renormalization group studies of SU(4) Kondo effect in quantum dots

We theoretically study an enhancement of the Kondo effect in quantum dots with two orbitals and spin . The Kondo temperature and conductance are evaluated as functions of energy difference Δ between the orbitals, using the numerical renormalization group method. The Kondo temperature is maximal around the degeneracy point (Δ=0) and decreases with increasing |Δ| following a power law, T_K(Δ)=T_K(0)(T_K(0)/|Δ|)^γ, which is consistent with the scaling analysis. The conductance at T=0 is almost constant 2e²/h. Both the orbitals contribute to the conductance around Δ=0, whereas the current through the upper orbital is negligibly small when |Δ|T_K(0). These are characteristics of SU(4) Kondo effect.     

金属中逆法拉第效应的经典理论

研究电子在圆偏振光驱动下的经典动力学问题以及金属中逆法拉第效应(IFE)的经典微观机制.得到电子在圆偏振光驱动下的一个解,表明其运动轨道是螺旋线.忽略电子与磁场的相互作用,电子作绕平行于其初速度的轴、横截面为椭圆的螺旋线运动,产生了一个平行于其初速度、方向由圆偏振光的手征性决定的磁矩.磁矩的统计结果与Hertel从电子气整体出发得到的结果一致.     

应变液晶的负压光效应和反式压光效应

介绍聚合物分散液晶和应变液晶概念,给出聚合物分散液晶调光玻璃的"正压光效应"、"负压光效应"和"反式压光效应"三种效应定义.实验制备出负压光效应和反式压光效应新型应变调光玻璃样品,测试样品散射态雾度90%以上,半透明态透光率接近30%.用偏光显微术研究压光效应原理,表明对样品施加垂面按压或拉伸的应力诱导作用会引起液晶微滴中液晶分子具有某些特殊排列方式,导致样品光学性质发生显著变化.建立垂面拉伸液晶微滴模型,计算模拟所绘出的图形与偏光显微镜照片独特花样十分相似,进而合理解释了实验现象.应变液晶压光效应研究具有聚合物分散液晶基础研究意义和开发非电控调光玻璃的实际应用价值.     

The leaving group dependence in the rates of solvolysis of 1,2‐diphenylethyl system

1,2‐Diphenylethyl chloride undergoes solvolysis by S_N1 mechanism in aqueous organic solvents. The α‐phenyl group of 1,2‐diphenylethyl chloride enters into conjugation with the developing carbocationic centre. The β‐phenyl group on the other hand was unable to extend its conjugation via neighbouring group participation due to steric inhibition of resonance in the formation of non‐classical carbocation. 1,2‐Diphenylethyl chloride thus behaves similar to 1‐phenylethyl chloride in its solvolysis pattern. The solvolytic rate studies of chloride and methanesulphonate of 1,2‐diphenylethyl alcohol in various aqueous organic solvents show that the dispersion observed in the Winstein–Grunwald plot is not due to a change in leaving group but due to the difference in solvation requirements of aromatic and aliphatic groups. Copyright © 2010 John Wiley & Sons, Ltd.     

Quantitative evaluation of high repetition rate laser jamming effect on the pulsed laser rangefinder

Laser may cause disfunction or even damage to laser rangefinder. Based on evaluation rules of high repetition rate laser jam pulsed laser rangefinder, the principles of distance deception and blinding jamming were analysed and the jamming success rate was calculated. We also set up a calculation example for 100 kHz repetition rate laser jam certain type rangefinder. The result showed that we can obtain jamming grade and success rate, accomplish the quantitative evaluation of the laser jamming effect.     

A rate equation of the laser that reflects the coherence of light

This paper presents a kind of rate equation of a laser governed by Feigenbaum's geometric relation of bifurcate gaps. New rate equations can not only describe the changing action of the laser output strength qualitatively, but can also reflect the coherence of light, and therefore reflect the relaxation of the equilibrium process of a laser to a certain degree.     

推广x重新标度模型重标度参数公式与轻子-核DIS过程的核效应

与原子核的平均结合能相联系，给出了部分子的推广x重新标度模型的重标度参数公式.利用该公式给出的重标度参数值，计算了铝核、钙核、铅核分别与碳核DIS过程的平均结构函数之比，结果表明理论计算与实验数据符合较好.     

Isospin effect of the in-medium nucleon-nucleon cross section in excited nuclear reactions

Using relativistic mean field theory, the neutron and the proton density distribution of 56Ni nuclei could be obtained in the ground state and the excited state. Based on the framework of the quantum molecular dynamics model, the 56Ni nuclei have been simulated in ground state and in the neutron or proton excited state. We then used the three different states of 56Ni to collide with the 56Ni in the ground state. To discuss the evolution of the nuclear stopping in different reactions, two kinds of different excited nuclear reactions were studied at different reaction energies and at different impact parameters. Studies have shown that the nuclear stopping of an excited nuclear reaction is sensitive to the isospin-dependent in-medium nucleon-nucleon cross section, compared with the response value of the ground state nuclear reaction. So, it is better for the excited nuclei to extract the isospin dependence of nucleon-nucleon cross section information.     

Isospin effect of the in-medium nucleon-nucleon cross section in excited nuclear reactions

Using relativistic mean field theory, the neutron and the proton density distribution of ⁵⁶Ni nuclei could be obtained in the ground state and the excited state. Based on the framework of the quantum molecular dynamics model, the ⁵⁶Ni nuclei have been simulated in ground state and in the neutron or proton excited state. We then used the three different states of ⁵⁶Ni to collide with the ⁵⁶Ni in the ground state. To discuss the evolution of the nuclear stopping in different reactions, two kinds of different excited nuclear reactions were studied at different reaction energies and at different impact parameters. Studies have shown that the nuclear stopping of an excited nuclear reaction is sensitive to the isospin-dependent in-medium nucleon-nucleon cross section, compared with the response value of the ground state nuclear reaction. So, it is better for the excited nuclei to extract the isospin dependence of nucleon-nucleon cross section information.     

The relationship between absorption coefficient and temperature and their effect on the atmospheric cooling rate

Several approaches are considered to determine the temperature effect on the absorption coefficient within a correlated k-distribution method. Taking in the 610- region for example, the absorption coefficients and atmospheric cooling rates calculated using these approaches are compared with line-by-line integration. It is emphasized in this paper by numerical calculation that the effect of pressure on absorption coefficient is related to temperature and vise versa; the larger the pressure, the larger the effect of temperature on absorption coefficient. Results show that the temperature effect must be considered in radiative calculations although its effect on the absorption coefficient is much smaller than that of pressure.     

Analysis of atom detection via the magnetic optical effect

We demonstrated a new method of atom detection by means of the magnetic optical effect. The number density of the atom cloud was measured by detecting the rotation angle of the polarization plane of linearly polarized probe light when propagating inside the atomic cloud. Detuning, the magnetic field and light intensity dependencies of the rotation angle were studied theoretically and experimentally to find the best parameter for atom detection. In this way, we managed to achieve a rotation angle of 0.22 rad with a signal to noise ratio (SNR) of 75 and a contrast of 87.5%.     

Numerical study of the effect of turbulence on rate of reactions in the MILD combustion regime

In this paper, the importance of fluctuations in flow field parameters is studied under MILD combustion conditions. In this way, a turbulent non-premixed CH₄+H₂ jet flame issuing into a hot and deficient co-flow air is modeled using the RANS Axisymmetric equations. The modeling is carried out using the EDC model to describe the turbulence-chemistry interaction. The DRM-22 reduced mechanism and the GRI2.11 full mechanism are used to represent the chemical reactions of H₂/methane jet flame. Results illustrate that although the fluctuations in temperature field are small and the reaction zone volume are large in the MILD regime, the fluctuations in temperature and species concentrations are still effective on the flow field. Also, inappropriate dealing with the turbulence effect on chemistry leads to errors in prediction of temperature up to 15% in the present flame. By decreasing of O₂ concentration of hot co-flow air, the effect of fluctuations in flow field parameters on flame characteristics are still significant and its effect on species reaction rates does not decrease. On the other hand, although decreasing of jet inlet Reynolds number at constant inlet turbulence intensity addresses to smaller fluctuations in flow filed, it does not lead to lower the effect of turbulence on species distribution and temperature field under MILD combustion conditions.     

Suppressing the hot carrier injection degradation rate in total ionizing dose effect hardened nMOSFETs

Annular gate nMOSFETs are frequently used in spaceborne integrated circuits due to their intrinsic good capability of resisting total ionizing dose (TID) effect. However, their capability of resisting the hot carrier effect (HCE) has also been proven to be very weak. In this paper, the reason why the annular gate nMOSFETs have good TID but bad HCE resistance is discussed in detail, and an improved design to locate the source contacts only along one side of the annular gate is used to weaken the HCE degradation. The good TID and HCE hardened capability of the design are verified by the experiments for I/O and core nMOSFETs in a 0.18 μm bulk CMOS technology. In addition, the shortcoming of this design is also discussed and the TID and the HCE characteristics of the replacers (the annular source nMOSFETs) are also studied to provide a possible alternative for the designers.     

电光晶体研究究进进展及其对称性性研研究

由电场引起的晶体折射率的变化称为晶体的电光效应,具有电光效应的晶体称为电光晶体。利用电光效应可以制作电光Q开关等重要光电器件。晶体的电光效应及其有效利用,均与其对称性密切相关。本文在综述电光晶体研究进展的基础上,推导了不同晶系中各晶类电光效应类型及其特点,并以电光Q开关的要求为例讨论了晶体的电光效应及其对称性之间的关系。从讨论结果得出:立方晶系Td-ˉ43m,三方晶系C3v-3m,四方晶系D2d-4ˉ2m,D4v-4mm和六方晶系D3h-6ˉm2,C6v-6mm点群中相应电光系数的横向或纵向效应可能有实用价值。在考虑旋光性影响后,立方晶系T-23,三方晶系D3-32,四方晶系中S4-4ˉ,六方晶系中C3h-6ˉ等也有可能应用。但是,电光晶体的应用与许多因素相关,对称性只是其中一个基本条件。     

光波位相耦合色散效应与固态介质中室温下的光速调控

文章介绍了作者利用光波位相耦合的色散效应调控光速的新机制，并利用光折变位相耦合的色散效应在室温下在Bi12SO20晶体中实现极慢光速和超光速现象．进一步的研究表明，在Bi12SO20晶体中传播的、由位相耦合色散效应引起的慢光和快光由于光折变光强耦合效应而得到了相干放大．     

硫醇自组装分子膜末端基团对其电荷输运特性的影响

在金(111)表面组装了具有不同末端基团的硫醇单层分子膜，并利用导电原子力显微镜研究了分子膜的电输运性质，发现不同末端基团的分子自组装膜的导电能力有明显差别.结合X射线光电子能谱，研究了末端基团中碳原子的结合能与相应硫醇分子电导的关系.结果表明不同末端基团分子膜导电能力的差别可归结为末端基团碳原子电子结合能的差异.结合能越高，末端基团电子的局域化程度越强，导致电子有效注入分子主链的势垒越高，从而减弱了分子膜对电子的输运能力.此外，实验还发现不同末端基团的硫醇单层分子膜有不同的表面电势，导致分子膜电流电压特性曲线的零点产生偏离. 关键词： 分子自组装膜 输运特性 末端基团 导电原子力显微镜     

The effect of the heating rate on the phase transition

ABSTRACT

The simple cubic spin-1 Ising model exhibits the ferromagnetic (F)–ferromagnetic (F) phase transition in the low temperature region for the interval 1.40 < d = D/J < 1.48 at k = K/J = –0.5. The degree of the F-F phase transition determines the special point on the (k_BT/J, d) phase diagram. In this paper, the critical behavior of the F-F phase transition was investigated for different heating rates using the cellular automaton heating algorithm. The universality class and the type of F-F phase transition were analyzed using the finite-size scaling theory and the power law relations. The results show that the F-F phase transition may be the second order, the first order or the weak first order depending on the heating rate in the interval 1.40 < d < 1.48 for k = –0.5.     

Reactivities of mixed organozinc and mixed organocopper reagents. Part 7. Comparison of the transfer rate of the same group in allylation of mixed and homo diorganozinc reagents

A detailed direct kinetic study has been carried out to compare the reaction rate of transferable group, Ph in mixed phenylzinc reagents, RPhZn (R = n‐alkyl) and in homo diphenylzinc reagent, Ph₂Zn in their reactions with allyl bromide in THF at 25–(?15) °C. Empirical rata law and activation parameters are consistent with a second‐order substitution reaction. The allylation rate of transferable group Ph in RPhZn (R = n‐alkyl) has been found higher than the rate of Ph group in Ph₂Zn. A mechanism which accommodates the kinetic data and higher allylation rate of transferable group Ph in RPhZn than that in Ph₂Zn is given. Copyright © 2013 John Wiley & Sons, Ltd.