A Vibrational Force Field For 1-Alkynes and Nitriles

Abstract

Normal coordinate calculations were made for 1-butyne, propionitrile, and the two conformers each of 1-pentyne and butyronitrile, using a thirty-one parameter modified valence force field. Only the triple bond stretching force constant was assumed to be different in the two families of compounds. Twenty force constants were refined to fit 117 frequencies of the six molecules, with the average error being 5.1 cm^?1, or 0.65%.     

Vibrational and Conformational Analysis of 5-Methyl-2-Hexyne

Infrared and Raman spectra were obtained for 5- methyl-2-hexyne and wereinterpreted with the aid of normal coordinate calculations. The spectra and molecular mechanics calculations show the compound to exist in two spectroscopically distinguishable stable conformations, with the C₁ conformer being only a little more stable than the C_s, conformer. Vibrational assignments were made for both conformers.     

Molecular dynamics simulation of the vapour → liquid transition of argon and the reaction coordinate of condensation

We have investigated the n-dependences of the rate constants of absorption and emission of monomers that are attached to and detached from the cluster of n monomers, and have determined n*, the number of monomers that form the critical nucleus of the homogeneous condensation of the Lennard-Jones?Ar vapour. The dynamics was clearly separated into two regions at the critical nucleus; n* did not, however, give the unique dividing point. The observed strong dependences of both the nucleus size and the barrier height of the nucleation on the induction time of the condensation suggest that a slowly changing variable instead of the cluster size is necessary as the reaction coordinate of the nucleation. Although the slow variable is not well characterised at the present stage of the investigation, it seems to be related to the local density of the gas atoms around the liquid-like clusters. Both the slow evolution of the radial distribution function of the gas atoms around the liquid-like atoms, and the correlation between n* and the onset of the condensation indicate that Gibbs energy curves represented in n-space change significantly with the activation of the slow variable.     

Scaled Quantum Chemical Studies of the Molecular Structure and Vibrational Spectra of Minoxidil

The Fourier transform Raman and Fourier transform infrared spectra for minoxidil have been recorded in the region 4000—100 cm^?1 and 4000—450 cm^?1, respectively. The structural and spectroscopy data of the molecule in the ground state were calculated by using density functional theory methods with 6-311G (d, p) basis set. A detailed vibrational analysis of the title compound has been done using normal coordinate analysis following the scaled quantum mechanical force field methodology. The calculated molecular geometry parameters and scaled vibrational wavenumbers are well compared with the experimental data. The electronic properties, such as excitation energies, absorption wavelength, highest occupied molecular orbital (HOMO), and lowest unoccupied molecular orbital (LUMO) energies were performed by time-dependent density functional theory approach, and the results are in good agreement with experimental absorption spectrum. The charge delocalizations of these molecules have been analyzed using natural bond orbital analysis. The molecule orbital contributions are studied by density of energy states. Fukui functions, local softness, and electrophilicity indices for selected atomic sites of the title compound are determined. Finally, the thermal behaviors of the compound have been calculated by different temperature.     

Vibrational and Conformational Analysis of 2-Methyl-1-butene

Normal coordinate calculations were made for 2-methyl-1-butene to aid in making vibrational assignments for both conformers. A partial solid-state IR spectrum was obtained that showed the presence of only the trans (C_s) conformer. Molecular mechanics and semi-empirical molecular orbital calculations were also made for both conformers.     

Vibrational Spectra,Normal Coordinate Calculations,and Molecular Mechanics Calculations for 2, 3, 3-Trimethyl-1-Butene

Infrared and Raman spectra were obtained for 2, 3, 3-trimethyl-1-butene, and a vibrational assignment was made with the aid of normal coordinate calculations. Molecular mechanics calculations were also made to determine molecular parameters of the stable conformation. Values for the force constants of a forty-one parameter modified valence force field were obtained that will be used for other 2-methyl-1-alkenes that contain substituted methyl groups.     

A non-destructive experimental investigation of elastic plastic interfaces of autofrettaged thick-walled cylindrical aluminium high pressure vessels

Positions of elastic plastic interfaces play a vital role in safe design and safe use of high pressure vessels. The ENGIN-X neutron diffractometer at the ISIS facility was used to measure the residual strain profiles in a series of aluminium vessels which had been subjected to different pressure levels. The positions of elastic plastic interfaces of the autofrettaged pressure vessels were identified. The results revealed that the residual strain magnitude and the depth of the plastic region will increase with increasing autofrettage pressure level. When autofrettage pressure produces an elastic-plastic boundary at a greater depth than the geometric mean position of the vessel wall, reverse yielding will occur, hence the loss of the vessels’ elastic ability to its subsequent loading. The neutron experimental results agreed well with both the suggestions from existing literatures and the results from FE simulations.     

炸药条加载圆柱壳的数值模拟（Ⅱ）：解耦分析与实验验证

 根据已报道的二维流固耦合数值模拟结果,建立了经缓冲橡胶整形后的单炸药条载荷模型。将炸药条载荷叠加后直接施加在圆柱壳表面,进行二维解耦模拟,得到了与流固耦合模拟基本吻合的应力结果。在此基础上,对19条炸药条加载Φ265 mm×380 mm圆柱壳进行了三维解耦模拟,并采用相同状态的实验予以验证。结果表明,特征点应变响应吻合较好,验证了炸药条加载圆柱壳解耦数值模拟的有效性,为大量工况数值分析、提高建模和计算效率奠定了基础。     

炸药柱面内爆磁通量压缩实验技术研究

炸药柱面内爆磁通量压缩实验技术 (MC-1) 是一种原理独特的高能量密度实验技术, 它是利用炸药内爆驱动金属套筒压缩其内部磁通量从而实现超高磁场, 利用超高磁场可以对其内部的样品实现等熵压缩. 由于这项技术具有超高磁场、等熵加载等特点, 在材料高压物性、新材料高压合成、及超强磁场下的凝聚态物理等多个领域都具有广阔的应用前景. 2011年, 中物院流体物理研究所在国内率先开展了这一方面的实验研究工作, 研制成功了单级MC-1实验装置, 观测到了MC-1实验的典型实验特征, 获得了超过430T的动态超强磁场. 数值分析表明, 利用这项技术可以实现对材料的等熵压缩. 这项技术的研究对于我国未来开展极端条件下的凝聚态物理研究具有积极的意义. 关键词： 柱面内爆 磁通量压缩 等熵压缩 超强磁场     

基于开槽单矩形栅和圆形电子注的W波段返波振荡器

提出将开槽单矩形栅和圆形电子注作为 W波段返波振荡器的注波互作用回路. 使用 3维电磁场仿真软件CST-MWS对开槽单矩形栅的高频特性进行了仿真分析, 研究结果表明: 相对于传统单矩形栅, 新结构的基模带宽有所展宽; 基模与高次模发生模式竞争的可能性很小; 在采用圆形电子注时新结构能获得大得多的耦合阻抗; 新结构的趋肤损耗略有改善. 将该慢波结构应用于设计一支以94 GHz为频带中心的W 波段返波振荡器: 设计了简洁的慢波过渡部分、输出耦合器和终端匹配衰减器, 优化参数后获得了良好的信号传输特性; 利用粒子模拟软件CST-PS对返波振荡器模型进行了三维大信号注波互作用计算, 设定合适的电子注电流等参数后, 调整工作电压在较宽的频带内获得了瓦级的功率输出, 电子效率在整个频带范围内优于1%. 关键词： 开槽单矩形栅 圆形电子注 返波振荡器 W波段