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1.
《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
2.
Stefan Weigert 《Czechoslovak Journal of Physics》2004,54(1):147-149
The eigenstates of a diagonalizable PT-symmetric Hamiltonian satisfy unconventional completeness and orthonormality relations. These relations reflect the properties of a pair of bi-orthonormal bases associated with non-hermitean diagonalizable operators. In a similar vein, such a dual pair of bases is shown to possess, in the presence of PT symmetry, a Gram matrix of a particular structure: its inverse is obtained by simply swapping the signs of some its matrix elements. 相似文献
3.
多小波子空间上的单小波表示 总被引:1,自引:0,他引:1
本文在较弱的条件下,建立了2重多小波子空间与单小波子空间的关系.即由2重多小波构造出单小波.一方面,这种单小波的平移伸缩与2重多小波的平移伸缩生成的子空间是完全相同的;另一方面,它具有插值性.因此通过构造出的单小波建立了多小波子空间上的Shannon型采样定理. 相似文献
4.
Banach空间上的框架与Riesz基 总被引:5,自引:0,他引:5
本文讨论Banach空间上框架、无冗框架与Riesz基之间的关系及它们的稳定性. 相似文献
5.
6.
Steen Ryom-Hansen 《Journal of Algebraic Combinatorics》2006,23(1):5-20
We generalize Soergel's tilting algorithm to singular weights and deduce from this the validity of the Lascoux-Leclerc-Thibon
conjecture on the connection between the canonical basis of the basic submodule of the Fock module and the representation
theory of the Hecke-algebras at root of unity.
Supported in part by Programa Reticulados y Ecuaciones and by FONDECYT grant 1051024. 相似文献
7.
J. J. EGOZCUE J. L. DIAZ-BARRERO V. PAWLOWSKY-GLAHN 《数学学报(英文版)》2006,22(4):1175-1182
The set of probability functions is a convex subset of L1 and it does not have a linear space structure when using ordinary sum and multiplication by real constants. Moreover, difficulties arise when dealing with distances between densities. The crucial point is that usual distances are not invariant under relevant transformations of densities. To overcome these limitations, Aitchison's ideas on compositional data analysis are used, generalizing perturbation and power transformation, as well as the Aitchison inner product, to operations on probability density functions with support on a finite interval. With these operations at hand, it is shown that the set of bounded probability density functions on finite intervals is a pre-Hilbert space. A Hilbert space of densities, whose logarithm is square-integrable, is obtained as the natural completion of the pre-Hilbert space. 相似文献
8.
Preconditioners based on various multilevel extensions of two‐level finite element methods (FEM) lead to iterative methods which have an optimal order computational complexity with respect to the size of the system. Such methods were first presented in Axelsson and Padiy (SIAM. J. Sci. Stat. Comp. 1990; 20 :1807) and Axelsson and Vassilevski (Numer. Math. 1989; 56 :157), and are based on (recursive) two‐level splittings of the finite element space. The key role in the derivation of optimal convergence rate estimates is played by the constant γ in the so‐called Cauchy–Bunyakowski–Schwarz (CBS) inequality, associated with the angle between the two subspaces of the splitting. It turns out that only existence of uniform estimates for this constant is not enough but accurate quantitative bounds for γ have to be found as well. More precisely, the value of the upper bound for γ∈(0,1) is part of the construction of various multilevel extensions of the related two‐level methods. In this paper, an algebraic two‐level preconditioning algorithm for second‐order elliptic boundary value problems is constructed, where the discretization is done using Crouzeix–Raviart non‐conforming linear finite elements on triangles. An important point to make is that in this case the finite element spaces corresponding to two successive levels of mesh refinements are not nested. To handle this, a proper two‐level basis is considered, which enables us to fit the general framework for the construction of two‐level preconditioners for conforming finite elements and to generalize the method to the multilevel case. The major contribution of this paper is the derived estimates of the related constant γ in the strengthened CBS inequality. These estimates are uniform with respect to both coefficient and mesh anisotropy. To our knowledge, the results presented in the paper are the first such estimates for non‐conforming FEM systems. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
9.
Yanghyun Byun 《Foundations of Physics》2004,34(6):987-1003
We consider a representation of the state reduction which depends neither on its reality nor on the details of when and how it emerges. Then by means of the representation we find necessary conditions, even if not the sufficient ones, for a decomposition of the state vector space to be a solution to the basis problem. The conditions are that the decomposition should be Lorentz invariant and orthogonal and that the associated projections should be continuous. They are shown to be able to determine a decomposition in each of a few examples considered if the other circumstances are taken into account together. 相似文献
10.
In the present work we consider the problem of interpolating scattered data using radial basis functions (RBF). In general, it is well known that this leads to a discrete linear inverse problem that needs to be regularized in order to provide a meaningful solution. The work focuses on a metric-regularization approach, based on a new class of RBF, called anisotropic RBF. The work provides theoretical justifications for the regularization approach and it considers a suitable proposal for the metric, supporting it by numerical examples. 相似文献