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Wolfgang K. Schubert J.F. Southern Lothar Schäfer 《Journal of Molecular Structure》1973,16(3):403-415
The structure of cis-1,4-ditertiarybutylcyclohexane(DTBC) was investigated by combined electron diffraction, conformational and vibrational analyses in order to obtain results which are more conclusive than those previously obtained by electron diffraction alone. In this study, first the minimum energy conformations for DTBC were calculated by the Westheimer-Hendrickson procedure using various force fields described in the literature; the same fields and the minimum energy conformations were used in subsequent vibrational analyses to calculate the mean amplitudes of vibration for each minimum energy conformation of DTBC; these mean amplitudes and the corresponding internuclear distances were then used to calculate the theoretical electron diffraction radial distribution curves which were compared to the experimental curves. The results indicate that the conformational energies of all the minimum energy chair and non-chair forms of DTBC are very similar. In excellent agreement with this, the theoretical radial distribution curves of all minimum energy forms have to be mixed for a best fit to the experimental radial distribution curve. A least squares analysis of the mixture under the described conditions yields for 110 °C a composition of approximately one third chair and two thirds non-chair forms. The quality of the empirical conformational force fields has a definite influence on the reliability of these results. 相似文献
4.
New Experimental Insight into the Nature of Metal−Metal Bonds in Digallium Compounds: J Coupling between Quadrupolar Nuclei 下载免费PDF全文
Dr. Libor Kobera Scott A. Southern Dr. Gyandshwar Kumar Rao Prof. Dr. Darrin S. Richeson Prof. Dr. David L. Bryce 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(28):9565-9573
Multiple bonding between atoms is of ongoing fundamental and applied interest. Here, we report a multinuclear (1H, 13C, and 71Ga) solid‐state magnetic resonance spectroscopic study of digallium compounds which have been proposed, albeit somewhat controversially, to contain single, double, and triple Ga?Ga bonds. Of particular relevance to the nature of these bonds, we have carried out two‐dimensional 71Ga J/D‐resolved NMR experiments which provide a direct measurement of J(71Ga,71Ga) spin–spin coupling constants across the gallium?gallium bonds. When placed in the context of clear‐cut experimental data for analogous singly, doubly, and triply bonded carbon spin pairs or boron spin pairs, the 71Ga NMR data clearly support the notion of a different bonding paradigm in the gallium systems. Our findings are consistent with an increasing role across the purported gallane–gallene–gallyne series for classical and/or slipped π‐type bonding orbitals. 相似文献
5.
The depolarisation ratio for the Raman-active phenyl stretching mode has been measured over the whole of the mesophase range,
and the orientational order parameters deduced, in the uniaxial nematic liquid crystal octylcyanobiphenyl (8CB). Linearly
polarised light was incident normally on a homogeneously aligned sample and a χ2 minimisation routine performed on the 360° depolarisation ratio profile. The order parameters 〈P
200〉 and 〈P
400〉 , together with the differential polarisability ratio, r , are used as fitting parameters and measured as a function of temperature. Interestingly, we show that the value for r , conventionally measured in the isotropic phase and assumed to remain constant, has a clear temperature dependence, ranging
from -0.032±0.008 in the isotropic phase through to -0.245±0.015 at the nematic-to-smectic A phase transition. The measured
order parameters 〈P
200〉 and 〈P
400〉 varied from 0.35- 0.55±0.02 and 0.180- 0.245±0.02 , respectively, across the 8 ° C wide nematic phase range. The values of both 〈P
200〉 and 〈P
400〉 are in excellent agreement with theory, but it is noteworthy that 〈P
400〉 shows a much better quantitative match than has been reported in previous work. Crucially the temperature dependence of
r is shown to be a contributing factor in the low 〈P
400〉 values that have been conventionally reported from Raman scattering measurements. The potential for fitting the entire angular
depolarisation ratio distribution in liquid crystalline systems that are described by more order parameters, specifically
biaxial materials, is discussed. 相似文献
6.
B. W. Southern 《Zeitschrift für Physik B Condensed Matter》1978,30(1):61-64
The interface free energy of an Ising model with nearest neighbour interactions on a generalized square lattice is calculated using a simple method suggested by Müller-Hartmann and Zittartz. For certain values of the coupling constants this lattice can be made to be topologically equivalent to either a hexagonal or triangular lattice. The method of calculation bypasses the full bulk problem by considering only special interface configurations of the spins. It is shown that a large number of exactly known results for these different types of lattice can be obtained using this simple method. 相似文献
7.
The morphology of high-density polyethylene crystallized under simultaneous pressure and shear in an Instron capillary viscometer has been examined by scanning electron microscopy, electron microscopy, and selected-area electron diffraction. Two distinct fibrous morphologies were observed in these unusually transparent strands. The outer sheath was composed of fibers, 3000 Å in diameter, aligned parallel to the extrusion direction and apparently interconnected by a lamellar cross texture. A highly crystalline ribbon texture composed of fine fibers, 200–250 Å in diameter, dominated the inner core. Sharp-spot electron diffraction patterns obtained from these central ribbons indicated a high degree of c-axis orientation parallel to the fibers and an extended-chain crystal structure. The melting behavior of both irradiated and unirradiated strands examined by differential scanning calorimetry was consistent with the formation of two distinct crystalline morphological units. 相似文献
8.
The isochronal annealing of the damage produced by thermal neutron irradiation of cadmium at 3.6 °K has been studied for several initial doses which vary by a factor of 1000. The recovery results show a strong dependence upon initial dose. This effect, which is not seen to this extent in the fcc metals, cannot be accounted for by an irradiation annealing mechanism. In contrast to the observation of two processes involving long range defect migration for several fcc metals only one process, at high temperatures, is discernable from isochronal annealing of Cd. The presence of another process at low temperatures is clearly established by other means. Irradiation annealing effects observed during the production of damage at high defect concentrations indicate that the spontaneous annihilation volume between the defects of a new capture event and the defects from an earlier event is 80 atomic volumes. Other results suggest that damage production and recovery mechanisms may be associated with the anisotropic nature of the cadmium hexagonal lattice. 相似文献
9.
反应型三元铕配合物的合成及发光性能研究 总被引:4,自引:0,他引:4
文章以邻菲咯啉为第一配体 ,顺丁烯二酸酐、丙烯腈、十一烯酸、油酸和亚油酸为活性第二配体 ,合成了 5种新的反应型三元铕配合物。通过元素分析 ,EDTA配位滴定分析 ,红外、紫外和荧光光谱分析 ,对标题配合物的组成和结构进行了表征 ,并研究了它们的发光性能。结果表明 ,5种新的反应型三元配合物与相应的二元配合物相比发光强度大大提高 ,反应型配体产生“协同效应”的能力为 :亚油酸 >油酸 >丙烯腈 >顺丁烯二酸酐 >十一烯酸。且配合物中引入了能与其他单体共聚的活性第二配体 ,为合成具有优异发光性妮的键合型稀土高分子功能材料提供了一条新的途径 相似文献
10.
Ke Xin Huang Yu Bing Feng Wei Yao Lei Xiang Yang Feng Wang Hai Bo Li Su Zeng Jing Xu Gong Ming Hui Hu Yu Zhao Xiu Mei Wu Xiao Kun Li Jia Qu 《中国化学快报》2009,20(10):1187-1190
Four naturally rare 5,6,7-trimethoxy-2,3-cis-dihydroflavonols(3-6) and two 5,6,7-trimethoxy-2,3-trans-dihydroflavonols(7-8) were designed and synthesized.Their antioxidative properties were evaluated by way of examining their scavenging capacities towards DPPH and O_2~(·-) free radicals,as well as by measuring their inhibitory ability against LPO.Both the 2,3-trans and the 2,3- cis conformers exhibited certain quenching abilities to DPPH and O_2~(·-) radicals,while most of the synthetic dihydroflavonols ... 相似文献