Quantum chemical study of several monocyclic complex β‐lactam C‐3, C‐4, and N‐derivatives,and β‐ring model molecules

A quantum chemical study of several complex monocyclic 4‐benzoyl‐4‐phenyl‐β‐lactam derivatives was carried out using cyclobutane, azetidine, 2‐azetidinone, 1‐methyl‐2‐azetidinone, and 3‐methyl‐2‐azetidinone as model compounds. The optimum geometry was obtained for the different conformations. The planarity of the ring was discussed in terms of the influence of the substituents on the amide resonance. To better analyze the amide resonance and the activity of the β‐lactam ring, a vibrational study was also carried out. To examine the influence of solvent polarity on the carbonyl bands, the Fourier transform–infrared (FT‐IR) spectra of the β‐lactam monocyclic derivatives were recorded in CCl₄, C₆H₆, and CHCl₃ solutions. The normal vibrations of the β‐lactam ring in the model compounds were characterized and used in the analysis of the β‐ring of more complex derivatives. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002     

四唑及其衍生物的理论研究Ⅷ: 硝氨四唑衍生物的从头算

运用从头计算法,在HF/6-31G^*水平下,全优化计算了7种硝氨四唑衍生物的分子几何和电子结构。结果表明,标题物的四唑环近似为平面构型;2H式中性分子的芳香性大于相应的1H式异构体。5-硝氨-1H四唑分子内氢键使硝氨基与环共面;其余标题物中硝氨基与环垂直。不同水平下的总能量计算表明,标题物中电子相关效应显著;1H式中性分子较2H式的能量高,5-硝氨四唑负离子在三个负离子中最稳定。根据电荷分布阐明了四唑环质子化位置和标题物与金属的配位方式。此外还计算了各标题物的红外光谱及热力学性质。     

Radical addition reactions: factors determining the transition-state geometry

Interatomic distances in the reaction centers of the addition reactions of (i) H^· to the C=C, C=O, N≡C, and C≡C bonds, (ii) ^·CH₃ radical to the C=C, C=O, and C≡C bonds, and (iii) alkyl, aminyl, and alkoxyl radicals to olefin C=C bonds were determined using a new semiempirical method for calculating transition-state geometries of radical reactions. For all reactions of the type X^· + Y=Z → X— Y—Z^· the r ^# _X...Y distance in the transition state is a linear function of the enthalpy of reaction. Parameters of this dependence were determined for seventeen classes of radical addition reactions. The bond elongation, Δr ^# _X...Y, in the transition state decreases as the triplet repulsion, electronegativity difference between the atoms X and Y in the reaction center, and the force constant of the attacked multiple bond increase. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 894–902, April, 2005.     

On the automatic restricted-step rational-function-optimization method

The rational function optimization algorithm is one of the widely used methods to search stationary points on surfaces. However, one of the drawbacks of this method is the step reduction procedure to deal with the overstepping problem. We present and comment on a method such that the step obtained from the solution of the rational function equations possesses the desired correct length. The analysis and discussion of the method is mainly centered on the location and optimization of transition states. Received: 18 June 1998 / Accepted: 17 September 1998 / Published online: 23 November 1998     

Ru_n(n=2~8)金属团簇的结构和能级分布的DFT研究

采用密度泛函理论中的广义梯度近似(DFT/GGA)方法,对Run团簇(n = 2~8)的几何结构与稳定性、束缚能以及能级分布的关系进行了研究,并分析了随着团簇原子数的增加,团簇的几何结构和费米能级的变化,结果表明:Ru簇的几何结构在4个原子以前是平面结构,而从5个原子开始为空间立体的稳定结构,束缚能随金属原子数的增加而增加。能级结构呈明显的分立特征,费米能级随原子个数的增加而增加,但从Ru7开始又有所降低,且团簇的能量间隙逐渐减小,趋近于大块金属的能级特征。     

N-苄叉基-1-氨基-萘及其类似物的构象与分子扭曲的共轭 驱动力

确定了N-[(4-二甲基氨基)-苄叉基]-2-氨基苯并咪唑(1)，N-[(4-二甲基氨基)-苄叉基]-2-氨基苯并噻唑(2)和N-苄叉基-1-氨基-萘(3)的晶体结构。利用AM1，RHF，DFT方法和STO-3G,4-31G,6-311G及6-311G基组，优化每个分子的23个扭曲构象(θ=0°～-89°)。尽管不同方法得到的最优构象的扭角不同，分子扭曲的驱动力总是起因于电子作用，在任一分子、任何电子态中，离域的π体系总是失稳定的，全平面构象不是π体系最稳定的构象。π电子的离域是分子扭曲的驱动力之一，与经典观点相反，非键原子间的核排斥作用是分子扭曲的阻力，而不是动力。     

硝酸酯分子几何构型的量子化学研究

运用MINDO / 3、MNDO 和AM1 三种半经验分子轨道(MO)方法, 通过SCF计算, 首次系统地获得了32个硝酸酯化合物分子的全优化几何构型。三种方法的计算结果与已报道的四个化合物(硝酸甲酯、吉纳、硝化甘油和太安)的实验结果相比, AM1法较好。所有硝酸酯的酯基(-ONO~2)具有近似不变的几何参数。直链烷基硝酸酯的键长和键角极为相近, 全部重原子均共平面。二元直链和四元硝酸酯具有对称的分子构型。     

Reachable and controllable sets for two-dimensional,linear, discrete-time systems

We consider two-dimensional discrete-time linear systems with constrained controls. We propose a simple polynomial time procedure to give an exact external representation of theN-step reachable set and controllable set. The bounding hyperplanes are explicitly derived in terms of the data of the problem. By using a result in computational geometry, all the calculations are made in polynomial time in contrast to classical methods. The limit case asN is also investigated.     

Changes in the conformational parameters of 1-allylbenzotriazole in a mixed halide π-complex [CuCl0.85Br0.15(C6H4N3CH2=CH2)] under the action of bromine atoms

Single crystals of [CuCl_0.85Br_0.15(C₆H₄N₃CH₂=CH₂)] (I) were obtained by alternating current electrochemical synthesis; their X-ray structural investigation has been carried out (DARCh automatic diffractometer, MoK _α radiation, θ/2θ scanning; 1460 reflections with F ≥ 4σ(F), R = 0.0517). The crystals are monoclinic, their space group is P2₁/c, a = 7.292(3) Å, b = 17.947(8) Å, c = 7.398(4) Å, β = 93.56(4)°, V = 966(1) ų, Z = 4). Complex I is close in structure to the previously investigated compound [CuCl(C₆H₄N₃CH₂=CH₂)] (II). In both structures, the trigonal-pyramidal surroundings of the copper atom include two halide atoms (one is apical), a nitrogen atom, and a C=C group. The Cu₂X₂ dimers are associated into {[Cu₂X₂(C₆H₅N₃CH₂=CH₂)]}_n layers due to the bridging function of the 1-allylbenzotriazole molecule. In spite of the similar coordination polyhedra of the metal atoms and identical bridging function of the ligand molecule in I and II, the differences in the conformation parameters of the allyl group π-coordinated by the copper(I) atom (trans-like in I and cis-like in II) caused by the presence of bromine atoms in the coordination sphere predetermine different structures of the organometallic [Cu₂X₂(C₆H₅N₃CH₂=CH₂)]₄ tetramer subunits in the layers and, as a consequence, formation of different crystal structures. Original Russian Text Copyright ? 2005 by E. A. Goreshnik, B. M. Mykhalichko, and V. N. Davydov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 1, pp. 174–178, January–February, 2005.     

靶场光测多站图像多目标判读技术

靶场光测图像处理的一个突出难题是如何分辨图像上出现的大量小目标。利用单站序列图像上目标的运动关联、目标在多站图像上像点之间的对极几何约束关系,提出了靶场多站图像多目标判读的新技术,采用单站序列图像目标卡尔曼运动轨迹预测及跟踪识别技术,以及多站图像对极几何约束同名目标匹配技术,突破了传统方法仅进行单站图像判读的局限。仿真结果证明其能有效解决多站、多目标的判读问题,已成功应用于我们研制的多套靶场图像判读系统中。