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81.
Shawn Shih 《中国化学会会志》2003,50(4):815-822
A large class of stereochemcial and related interactions in organic chemistry are repulsive and others are attractive, but the relative orientation of two methyl groups and the amount of energy required to twist one relative to the other (the hindered rotation energy barriers), or the alignment of such a group with respect to a conjugated ring to which it is attached (widely attributed to a mechanism called “hyperconjugation”) are estimated to be small in compared with the total energy of the molecule. We used theories of both isotropic and anisotropic proton hyperfine interactions in the π‐electron systems developed in the early sixties. They are approximated by the magnetic dipole nteractions between each proton and an electron spin magnetization that is distributed in 2s and 2p Slater atomic orbitals center on carbon atoms. We have extended these theories to the non‐planar olefinic cation radicals, which are very important in biochemistry as well as in petroleum catalysis. A three dimensional electron spin density equation has been developed in this paper to handle some Jahn‐Teller vibronic molecules. The new electron spin density equation related the observed proton hyperfine splittings to the non‐planar structures of the open‐chain alkene cation radicals generated by radiolysis and various chemical oxidation methods. The spin densities and the conformational calculations based on valence bond theory and symmetry principles are compared with some more elaborated molecular orbital calculations in the literature. The localized valence bond approaches are better in accord with our experimental results. The anomalous line‐width effect of the four methyl groups observed in the 2,3‐dimethyl‐2‐butene cation radicals also confirmed the positive sign of the electron‐proton hyperfine constant of hyper‐conjugation mechanism. A methyl substituent attached to a conjugated molecule often behaves as if it formed part of the region of conjugation; the charge appears to flow from the methyl group into the π electron system and it may also give rise to an appreciable dipole moment. Methylation also gives rise to an appreciable dipole moment, and the resultant red shift of electronic absorption bands is of some importance in the design of dye molecules. 相似文献
82.
A finite element solution of the Navier-Stokes equations for steady flow under the magnetic effect through a double-branched two-dimensional section of a three-dimensional model of the canine aorta is discussed. The numerical scheme involves transforming the physical co-ordinates to a curvilinear boundary-fitted co-ordinate system. The shear stress at the wall is calculated for a Reynolds number of 1000 with the branch-to-main aortic flow rate ratio as a parameter. The results are compared with earlier works involving experimental data and found to be in reasonable qualitative agreement. The steady flow, shear stress and branch flow under the effect of a magnetic field have been discussed in detail. 相似文献
83.
Deák L. Bottyán L. Major M. Nagy D. L. Spiering H. Szilágyi E. Tanczikó F. 《Hyperfine Interactions》2002,144(1-4):45-52
Hyperfine Interactions - Synchrotron Mössbauer Reflectometry (SMR), the grazing incidence nuclear resonant scattering of synchrotron radiation, can be applied to perform depth-selective phase... 相似文献
84.
The methods for the few-body system are introduced to investigate the states of the barrier Li quantumdots (QDs) in an arbitrary strength of magnetic field. The configuration, which consists of a positive ion located on thez-axis at a distance d from the two-dimensional QD plane (the x-y plane) and three electrons in the dot plane boundby the positive ion, is called a barrier Li center. The system, which consists of three electrons in the dot plane bound bythe ion, is called a barrier Li QD. The dependence of energy of the state of the barrier Li QD on an external magneticfield B and the distance d is obtained. The angular momentum L of the ground states is found to jump not only withthe variation of B but also with d. 相似文献
85.
Emulsions of perfluorotributylamine (FTBA) and perflubron were evaluated for their utility in 19F echo planar imaging. Fluorine images of the emulsions were obtained in a phantom and two mice that had been predosed. Both agents, but particularly perflubron, show potential for fluorine echo planar studies because of the long spin-spin relaxation times of the CF3 resonances. High resolution thin slice images obtained in as little as 26.6 ms are presented. 相似文献
86.
We derive and analyse four algorithms for computing the current induced on a thin straight wire by a transient electric field.
They all involve solving the thin wire electric field integral equations (EFIEs) and consist of a very accurate differential
equations solver together with various schemes to approximate the vector potential integral equation. We carry out a rigorous
numerical stability analysis of each of these methods. This has not previously been done for solution schemes for the thin
wire EFIEs. Each scheme is shown to be stable and convergent provided the radius of the wire is small enough for the thin
wire equations to be a valid model. 相似文献
87.
Keka Chakraborty S K Paranjpe V Siruguri O D Jayakumar S K Kulshreshtha 《Pramana》1997,48(6):1115-1122
Neutron diffraction and M?ssbauer measurements have been carried out on the cubic Laves phase intermetallic TbMnFe. The magnetic
moment on the transition metal atom is found to be low, 0.2μ
B, at room temperature. This moment is temperature independent down to 10 K. Magnetic moment on the rare earth atom varies
from 2.5μ
B at 296 K to 7.27μ
B at 10 K. M?ssbauer spectra recorded at 298 K and 78 K have magnetic character but there is a large distribution of hyperfine
field values. Both these features arise due to magnetic frustration created in the sample due to the competing ferro and antiferromagnetic
interactions between the transition metal atoms. 相似文献
88.
S. Chen H. Büttner 《The European Physical Journal B - Condensed Matter and Complex Systems》2002,29(1):15-18
We generalize the Shastry-Sutherland model to three dimensions. By representing the model as a sum of the semidefinite positive
projection operators, we exactly prove that the model has exact dimer ground state. Several schemes for constructing the three-dimensional
Shastry-Sutherland model are proposed.
Received 20 February 2002 / Received in final form 27 May 2002 Published online 17 September 2002 相似文献
89.
REN QingBao ZHU WeiTing HONG Bo & ZHANG YuHeng Department of Physics Lishui University Lishui China National High Magnetic Field Laboratory University of Science Technology of China Hefei China 《中国科学G辑(英文版)》2007,(3)
Magnetic properties of Nd_(0.5)Sr_(0.5)Mn_(1-x)(Ga_x, Ti_x)O_3 system (0.04≤x≤0.4) were inves- tigated through magnetization and electron spin resonance (ESR) measurements. It was observed that a small amount of Ti substitution for Mn will destroy the charge-ordering (CO) phase completely and induce the cluster-spin-glass phase in the system, which displays a procedure of collapse of CO and of an enhancement of spin ordering (SO) phase. In contrast, the Ga substitution for Mn induces a melt- ing of CO phase in the system. It was observed that with substitution the CO phase is suppressed gradually and the remanent CO phase is retained all the while, and withal, there is a co-existence of AFM CO phase and FM SO at low temperature. In addition, an abrupt rise of magnetization was observed in M-T curves. We attributed this abnormal phenomenon to a transition from canted AFM SO to FM SO in CO region. 相似文献
90.
A. I. Golovashkin G. N. Izmaïlov G. V. Kuleshova T. Q. Khánh A. M. Tskhovrebov L. N. Zherikhina 《The European Physical Journal B - Condensed Matter and Complex Systems》2007,58(3):243-249
A scheme of magnetic calorimeter for registration of rare events
characterized by small energy release (cosmic rays, WIMPs, solitary X-ray
quanta) is proposed. The calorimeter is brought to operation by adiabatic
demagnetization, and its magnetic response is measured by a quantum
interferometer (SQUID, A. Barone and G. Paterno, Physics and applications of Josephson Effect). Special consideration is given to the specific
features of calorimeter operation in the ferromagnetic transition region.
The trigger registration of ultrasmall energy release by a ferromagnetic
system in the metastable state is described. 相似文献