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41.
42.
Akimoto Tachibana Masahiko Koizumi Iwao Okazaki Hiroyuki Teramae Tokio Yamabe 《Theoretical chemistry accounts》1987,71(1):7-19
The non- and fluorine-substituted singlet carbonyl ylides are studied by using ab initio MCSCF calculations. The thermodynamic stability of the carbonyl ylides and the intramolecular stability to isomerization or fragmentation reaction coordinates is demonstrated in terms of the topological structure of the ab initio potential energy surfaces. The allylic resonance is found to be dynamically unstable, considering out-of-plane vibrational mode. The instability is studied by the symmetries of the low-lying excitations out of the MCSCF wave function. 相似文献
43.
An amperometric detector with a small thin mercury film electrode is described. The device demonstrates advantageous operational
characteristics such as small dispersion (D<2) and “memory effect” (me<0.6%), extensive maximum sample frequency (msf −200
samples/h), and high sensitivity. It has been proven useful in flow-injection analysis at a constant potential under hydrodynamic
conditions. 相似文献
44.
在电子转移半经典模型的基础上,对氟代苯并菲组成的盘状液晶体系的电荷转移反应进行了研究,其反应动力学参数在量子化学B3LYP/6-31G(d,p)水平进行计算.研究中发现在反应物和产物的构型确定后,用线性反应坐标构造的反应途径和过渡态的构型不是唯一的.其原因是反应物和产物确定后,其独立内坐标的选择并不是唯一的.因此在计算电荷转移速率常数时必须考虑到多个过渡态构型才能得到定性正确的结果. 相似文献
45.
The apparent and limiting apparent molar volumes of dilute aqueous solutions of KBF4, and the complexes [Fe(DMSO)6](BF4)3, [Fe(Py)4(H2O)2](BF4)3, [Fe(4-Mepy)2(H2O)2](BF4)3, and [Fe(4-Etpy)2(H2O)2](BF4)3 were determined from density data measured at 5, 15, and 25°C. The apparent and limiting apparent molar adiabatic compressibilities of these complexes were determined from ultrasonic sound velocities measured at the same temperatures in dilute aqueous solutions. The volume change associated with complex formation is discussed in terms of the nature of the coordinate bond and also the role of the central metal atom and ligands in the solvation behavior of these complexes. 相似文献
46.
Hedi Hannachi Naoual Anoune Christian Arnaud Pierre Lant ri R mi Longeray Henry Chermette 《Journal of Molecular Structure》1998,434(1-3):183-191
The Baeyer-Villiger reaction of polymethoxybenzaldehydes with peroxysuccinic acid (PSA) is studied theoretically. The semi-empirical SCF-MO/PM3 method has been used to study the reaction and to calculate the energy profiles. In addition, heat of formation computations and bond order analyses of the transition species along the reaction coordinates have been performed and are interpreted qualitatively in terms of electron flow through the system during aryl migration. Our results support the hypothesis that the second step is a concerted reaction. Our data support a definite effect of the substituent on the aryl migration. The theoretical predictions are in good agreement with experimental results. 相似文献
47.
消臭抗菌纤维素纤维的制备、结构和性能 总被引:2,自引:0,他引:2
采用一种制备消臭、抗菌纤维素纤维的新方法,即先将纤维素纤维用多元羧酸进行化学修饰,然后在铜溶液中处理,生成铜螯合纤维素纤维,用红外光谱、电子自旋波谱表征了该纤维的配位结构,消臭和抗菌实验结果显示,这种功能性纤维对硫化氢,氢气、三甲胺的消臭率分别达到100%,92.1%和80.4%,对金黄色葡萄球菌,大肠杆菌和白色念珠菌的抑菌率分别为79.14%,93.59%和82.50%,用X射线衍射,电子自旋波谱分析了该纤维吸附硫化氢,氨气、三甲胺的机理。 相似文献
48.
49.
The boundary effect on the drag on two identical, nonuniformly structured flocs moving along the axis of a cylindrical tube
filled with a Newtonian fluid is investigated at a small to medium larger Reynolds number. A two-layer model is adopted to
simulate various possible structures of a floc, and the flow field inside is described by Darcy–Brinkman model. The results
of numerical simulation reveal that a convective flow is present in the rear region of a floc when Reynolds number is on the
order of 40. The presence of the tube wall and/or the porous structure of a floc has the effect of reducing that convective
flow. For a fixed level of the volume-average permeability of a floc, the influence of the tube wall on the drag depends upon
floc structure; the influence on a nonuniformly structured floc is more significant than that on a uniformly structured floc.
The more nonuniform the floc structure, the more appreciable the deviation of the drag coefficient–Reynolds number curve from
a Stokes’-law-like relation becomes. The smaller the volume-average permeability of a floc and/or the smaller the separation
distance between the two flocs, the greater is the deviation, but the presence of the tube wall has the effect of reducing
that deviation. 相似文献
50.
R. Pikl U. Posset S. Möller R. Lankat W. Malisch W. Kiefer 《Vibrational Spectroscopy》1996,10(2):161-167
In order to examine the influence of the transition metal on the metal-silyl fragment MSiH3 and the metal-silicon bond, polarized Raman spectra of the complexes (C5R5)(CO)2FeSiH3 R = H (Cp) (1a), Me (Cp*) (1b)], (C5H5)(CO)(PPh3)FeSiH3 (1c), (C5Me5)(CO)2RuSiH3 (2), (C5R5)(CO)2(PMc3)MoSiH3 [R = H (3a), Me (3b)], and (C5R5)(CO)2(PMe3)WSiH3 [R = H(4a), Me (4b)] have been recorded. The spectral data have been evaluated and interpreted on the basis of a normal coordinate analysis of the MSiH3 core and the derived force constants and potential energy distributions were compared to results obtained for analogous halogen derivatives in the series XSiH3 [X = Br (5), I (6)]. 相似文献