How Aromatic Fluorination Exchanges the Interaction Role of Pyridine with Carbonyl Compounds: The Formaldehyde Adduct

The rotational spectrum of the weakly bound complex pentafluoropyridine⋅⋅⋅formaldehyde has been investigated using Fourier transform microwave spectroscopy. From the analysis of the rotational parameters of the parent species and of the ¹³C and ¹⁵N isotopologues, the structural arrangement of the adduct has been unambiguously established. The full ring fluorination of pyridine has a dramatic effect on its binding properties: It alters the electron density distribution at the π-cloud of pyridine creating a π-hole and changing its electron donor-acceptor capabilities. In the complex, formaldehyde lies above the aromatic ring with one of the oxygen lone pairs, as conventionally envisaged, pointing toward its centre. This lone pair⋅⋅⋅π-hole interaction, reinforced by a weak C−H⋅⋅⋅N interaction, indicates an exchange of the electron-acceptor roles of both molecules when compared to the pyridine⋅⋅⋅formaldehyde adduct. Tunnelling doublets due to the internal rotation of formaldehyde have also been observed and analysed leading to a discussion on the competition between lone pair⋅⋅⋅π-hole and π⋅⋅⋅π stacking interactions.     

反应物振动量子数对O(~1D)+HBr→OH+Br立体动力学影响的研究

采用准经典轨线(QCT)方法计算了O(1D)+HBr→OH+Br反应体系的立体动力学反应.基于由Peterson(J.Chem.Phys.113(2000)4598)等人开发的基态势能面上,计算了反应的矢量相关性质,极角p(θ)r及方位角pφ()r以及空间角pθr,φ()r.此外我们还计算了极化微分反应截面(PDDCSs)的分布各矢量性质随各振动量子数变量的变化.结果表明反应受反应物振动量子数影响较大.     

基于小波高频距离像的红外小目标检测

针对远距离复杂背景下红外小目标检测问题,本文提出了一种基于小波高频距离像的方法。该方法首先将处理空间变换到小波域,通过分析残留背景、目标和噪声系数在高频子带的差异,定义基于邻域均值的子带系数表达形式,构造高频子带系数的中心向量,对小波高频图像进行综合形成距离像,得到红外复杂背景的抑制结果。在此基础上,利用恒虚警率算法将单帧背景抑制图像分割成候选目标、残留背景和噪声像素点。最后,在时间域基于目标运动的相关性,利用管道滤波实现红外小目标的最终检测。仿真实验结果表明,相对于经典算法,本文方法可以实现对红外复杂背景的有效抑制,增强目标信号的强度,准确稳定的从红外复杂背景中检测出小目标。     

防空导弹自动驾驶仪测试性建模研究与应用

为了得到防空导弹自动驾驶仪的故障检测与诊断策略,减少自动驾驶仪的测试费用,建立了自动驾驶仪的测试性模型并进行分析,解决了建模的难点。通过多层抽象混合推理故障建模方法推导了自动驾驶仪结构与测试点之间的关系,根据测试点的特征和自动驾驶仪工作原理建立信息流模型,在此基础上,利用故障与测试间的相关性矩阵来描述测试性模型。基于此模型设计了诊断策略构建方法。实际应用表明,建立测试性模型的方法完全正确,通过模型能够构建有效的检测与诊断策略,缩短测试时间。     

三线摆实验中摆角偏大产生的误差及修正方法

研究了三线摆实验中摆角偏大(5°θ20°)时对测量转动惯量产生的误差和修正办法。实验发现随着摆角的增大,测得的圆盘转动惯量也会相应偏大,从而导致测量误差增大。文章通过进一步的理论分析解释了这一现象,并对测量结果进行了系统误差修正。     

Probing the CH⋅⋅⋅π Weak Hydrogen Bond in Anesthetic Binding: The Sevoflurane–Benzene Cluster

Cooperativity between weak hydrogen bonds can be revealed in molecular clusters isolated in the gas phase. Here we examine the structure, internal dynamics, and origin of the weak intermolecular forces between sevoflurane and a benzene molecule, using multi‐isotopic broadband rotational spectra. This heterodimer is held together by a primary C? H???π hydrogen bond, assisted by multiple weak C? H???F interactions. The multiple nonbonding forces hinder the internal rotation of benzene around the isopropyl C? H bond in sevoflurane, producing detectable quantum tunneling effects in the rotational spectrum.     

Probing the Rotational Dynamics of meso‐(2‐Substituted)aryl Substituents in A2B‐Type Subporphyrins

A₂B‐type B‐methoxy subporphyrins 3 a – g and B‐phenyl subporphyrins 7 a – c , e , g bearing meso‐(2‐substituted)aryl substituents are synthesized, and their rotational dynamics are examined through variable‐temperature (VT) ¹H NMR spectroscopy. In these subporphyrins, the rotation of meso‐aryl substituents is hindered by a rationally installed 2‐substituent. The rotational barriers determined are considerably smaller than those reported previously for porphyrins. Comparison of the rotation activation parameters reveals a variable contribution of ΔH^≠ and ΔS^≠ in ΔG^≠. 2‐Methyl and 2‐ethyl groups of the meso‐aryl substituents in subporphyrins 3 e , 3 f , and 7 e induce larger rotational barriers than 2‐alkoxyl substituents. The rotational barriers of 3 g and 7 g are reduced by the presence of the 4‐dibenzylamino group owing to its ability to stabilize the coplanar rotation transition state electronically. The smaller rotational barriers found for B‐phenyl subporphyrins than for B‐methoxy subporphyrins indicate a negligible contribution of S_N1‐type heterolysis in the rotation of meso‐aryl substituents.     

On the Rotational Intergrowth of Hierarchical FAU/EMT Zeolites

A structural study of a hierarchical zeolite X, which is similar to the one first synthesized by Inayat et al., 12 was performed using transmission electron microscopy imaging and diffraction. Evidence is provided, by comparison to simulations, that this material is an intergrowth of FAU and EMT and a conceptual model is presented for the growth of the FAU material with a small fraction of EMT in an atypical morphology of assembled sheets with well‐defined intersection angles.     

The Scent of Maibowle – π Electron Localization in Coumarin from Its Microwave-Determined Structure

The microwave spectra of the natural substance coumarin, a planar aromatic molecule with the specific scent of maibowle, a popular fruit punch served in spring and early summer, were recorded using a molecular jet Fourier transform microwave spectrometer working in the frequency range from 4.0 to 26.5 GHz. The rotational constants and centrifugal distortion constants were determined with high precision, reproducing the spectra to experimental accuracy. The spectra of all singly-substituted ¹³C and ¹⁸O isotopologues were observed in their natural abundances to determine the experimental heavy atom substitution r_s and semi-experimental equilibrium r_e^SE structures. The experimental bond lengths and bond angles were compared to those obtained from quantum chemical calculations and those of related molecules reported in the literature with benzene as the prototype. The alternation of the C−C bond lengths to the value of 1.39 Å found for benzene reflects the localization of π electrons in coumarin, where the benzene ring and the lactone-like chain −CH=CH−(C=O)−O− are fused. The large, negative inertial defect of coumarin is consistent with out-of-plane vibrations of the fused rings.