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21.
《Magnetic resonance in chemistry : MRC》2003,41(6):417-430
A systematic study of the one‐bond and long‐range J(C,C), J(C,H) and J(H,H) in the series of nine bicycloalkanes was performed at the SOPPA level with special emphasis on the coupling transmission mechanisms at bridgeheads. Many unknown couplings were predicted with high reliability. Further refinement of SOPPA computational scheme adjusted for better performance was carried out using bicyclo[1.1.1]pentane as a benchmark to investigate the influence of geometry, basis set and electronic correlation. The calculations performed demonstrated that classical ab initio SOPPA applied with the locally dense Dunning's sets augmented with inner core s‐functions used for coupled carbons and Sauer's sets augmented with tight s‐functions used for coupled hydrogens performs perfectly well in reproducing experimental values of different types of coupling constants (the estimated reliability is ca 1–2 Hz) in relatively large organic molecules of up to 11 carbon atoms. Additive coupling increments were derived for J(C,C), J(C,H) and J(H,H) based on the calculated values of coupling constants within SOPPA in the model bicycloalkanes, in reasonably good agreement with the known values obtained earlier on pure empirical grounds. Most of the bridgehead couplings in all but one bicycloalkane appeared to be essentially additive within ca 2–3 Hz while bicyclo[1.1.1]pentane demonstrated dramatic non‐additivity of ?14.5 Hz for J(C,C), +16.6 Hz for J(H,H) and ?5.5 Hz for J(C,H), in line with previous findings. Non‐additivity effects in the latter compound established at the SOPPA level should be attributed to the through‐space non‐bonded interactions at bridgeheads due to the essential overlapping of the bridgehead rear lobes which provides an additional and effective non‐bonding coupling path for the bridgehead carbons and their protons in the bicyclopentane framework. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
22.
We establish a relation between stable distributions in probability theory and the fractional integral. Moreover, it turns out that the parameter of the stable distribution coincides with the exponent of the fractional integral. It follows from an analysis of the obtained results that equations with the fractional time derivative describe the evolution of some physical system whose time degree of freedom becomes stochastic, i.e., presents a sum of random time intervals subject to a stable probability distribution. We discuss relations between the fractal Cantor set (Cantor strips) and the fractional integral. We show that the possibility to use this relation as an approximation of the fractional integral is rather limited. 相似文献
23.
RUAN Manqi XU Gang & ZENG Jinyan Department of Physics Tsinghua University Beijing China Department of Physics Peking University Beijing China Correspondence should be addressed to Zeng Jinyan 《中国科学G辑(英文版)》2004,47(1):36-41
Foratwo-particle(spin1/2)systemthespinstateisdescribedusingavectorinafour-dimensionalHilbertspace.Inangularmomentumcouplingtheory[1],theangularmomentumuncouplingandcouplingrepresentationsareusuallyadopted.WhilethesimultaneouseigenstatesoftheCSCO(s1z,s2z),12,12,12and12,arechosenasthebasisofangularmomentumuncouplingscheme,thesimultaneouseigenstatesoftheCSCO(2,zSS),,SM(12=+Sss),arechosenasthebasisofangularmomentumcouplingscheme,1212100,2轾=-臌1212110,2轾=+臌121211,1,1.=-=Thefo… 相似文献
24.
On Best Approximations from RS-sets in Complex Banach Spaces 总被引:2,自引:0,他引:2
ChongLI 《数学学报(英文版)》2005,21(1):31-38
The concept of an RS-set in a complex Banach space is introduced and the problem of best approximation from an RS-set in a complex space is investigated. Results consisting of characterizations, uniqueness and strong uniqueness are established, 相似文献
25.
Omer Ozturk Steven N. MacEachern 《Annals of the Institute of Statistical Mathematics》2004,56(4):701-720
We develop a method of randomizing units to treatments that relies on subjective judgement or on possible coarse modeling
to produce restrictions on the randomization. The procedure thus fits within the general framework of ranked set sampling.
However, instead of selecting a single unit from each set for full measurement, all units within a set are used. The units
within a set are assigned to different treatments. Such an assignment translates the positive dependence among units within
a set into a reduction in variation of contrasting features of the treatments.
A test for treatment versus control comparison, with controlled familywise error rate, is developed along with the associated
confidence intervals. The new procedure is shown to be superior to corresponding procedures based on completely randomized
or ranked set sample designs. The superiority appears both in asymptotic relative efficiency and in power for finite sample
sizes. Importantly, this test does not rely on perfect rankings; rather, the information in the data on the quality of rankings
is exploited to maintain the level of the test when rankings are imperfect. The asymptotic relative efficiency of the test
is not affected by estimation of the quality of rankings, and the finite sample performance is only mildly affected. 相似文献
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A method for computing low Mach number flows using high‐resolution interpolation and difference formulas, within the framework of the Marker and Cell (MAC) scheme, is presented. This increases the range of wavenumbers that are properly resolved on a given grid so that a sufficiently accurate solution can be obtained without extensive grid refinement. Results using this scheme are presented for three problems. The first is the two‐dimensional Taylor–Green flow which has a closed form solution. The second is the evolution of perturbations to constant‐density, plane channel flow for which linear stability solutions are known. The third is the oscillatory instability of a variable density plane jet. In this case, unless the sharp density gradients are resolved, the calculations would breakdown. Under‐resolved calculations gave solutions containing vortices which grew in place rather than being convected out. With the present scheme, regular oscillations of this instability were obtained and vortices were convected out regularly. Stable computations were possible over a wider range of sensitive parameters such as density ratio and co‐flow velocity ratio. Copyright © 2004 John Wiley Sons, Ltd. 相似文献