Non‐empirical calculations of NMR indirect carbon–carbon coupling constants. Part 4: Bicycloalkanes

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.     

The Maximal Closed Classes of Unary Functions in p-Valued Logic

In many-valued logic the decision of functional completeness is a basic and important problem, and the thorough solution to this problem depends on determining all maximal closed sets in the set of many-valued logic functions. It includes three famous problems, i.e., to determine all maximal closed sets in the set of the total, of the partial and of the unary many-valued logic functions, respectively. The first two problems have been completely solved ([1], [2], [8]), and the solution to the third problem boils down to determining all maximal subgroups in the k-degree symmetric group S_k, which is an open problem in the finite group theory. In this paper, all maximal closed sets in the set of unary p-valued logic functions are determined, where p is a prime. Mathematics Subject Classification: 03B50, 20B35.     

Basis Set Orbital Relaxation in Atomic and Molecular Hydrogen Systems

Orbital relaxation (OR) amounts to variation of the orbital exponents in hydrogen molecules and ions relative to the exponents of the isolated atom; it is represented as the sum of the one- and two-center contributions depending on the effective atomic charge and on the presence of other atoms in the molecule. The procedure for isolating the contributions of the exponent includes treatment of the OR of hydrogen in a special set of neutral and charged atoms and molecules with certain multiplicities of their electronic states. Within the framework of the spin-unrestricted Hartree-Fock method, we found and discussed the optimal values of the exponents of the basis orbitals of hydrogen atoms and molecules using the minimal split valence-shell basis set, the basis set that includes the polarization function, and the expanded set of grouped natural orbitals. A simple energy model is suggested for OR. Expressions are derived for evaluating the exponents of the relaxed orbitals in hydrogen-containing systems.Original Russian Text Copyright © 2004 by A. I. Ermakov, A. E. Merkulov, A. A. Svechnikova, and V. V. Belousov__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 973–978, November–December, 2004.     

A least‐square weighted residual method for level set formulation

In this paper, a least‐square weighted residual method (LSWRM) for level set (LS) formulation is introduced to achieve interface capturing in two‐dimensional (2D) and three‐dimensional (3D) problems. An LSWRM was adopted for two semi‐discretized advection and reinitialization equations of the LS formulation. The present LSWRM provided good mathematical properties such as natural numerical diffusion and the symmetry of the resulting algebraic systems for the advection and reinitialization equations. The proposed method was validated by solving some 2D and 3D benchmark problems such as those involving a rotating slotted disk, the rotation of a slotted sphere, and a time‐reversed single‐vortex flow and a deformation problem of a spherical fluid. The numerical results were compared with those obtained from essentially non‐oscillatory type formulations and particle LS methods. Further, the proposed LSWRM for the LS formulation was coupled with a splitting finite element method code to solve the incompressible Navier–Stokes equations, and then, the collapse of a 3D broken dam flow was well simulated; in the simulation, the entrapping of air and the splashing of the surge front of water were reproduced. The mass conservation of the present method was found to be satisfactory during the entire simulation. Copyright © 2011 John Wiley & Sons, Ltd.     

关于Halpern的一个定理

设M是闭的.连通的,光滑的m形,m>2, f映射,P二}xEM[f'(二)=二,对某个;,15r2的周期 本文利用复迭空间的概念推广     

软件管道化方法

用完全数据关联图CDG来表述软件管道化问题,图中有向边表示循环中各指令间的关联性,同时提出了基础集的概念,平行可扩展的基础集可以覆循环的指令,文中用遗传算法来搜索基础集的最优解或次最优解,这种方法可以处理所有可能的数据关联性,从而可以将循环高度并行化。     

Dynamical linked cluster expansions with applications to disordered systems

Dynamical linked cluster expansions are linked cluster expansions with hopping parameter terms endowed with their own dynamics. We discuss physical applications to systems with annealed and quenched disorder. Examples are the bond-diluted Ising model and the Sherrington-Kirkpatrick spin glass. We derive the rules and identify the full set of graphs that contribute to the series in the quenched case. This way it becomes possible to avoid the vague extrapolation from positive integer n to n = 0, that usually goes along with an application of the replica trick. Received 13 December 2001 Published online 25 June 2002     

A unified theory for coherent systems in reliability part III: Two special cases for multinary systems—binary-type coherence and homogeneous coherence

As shown in a companion-paper,¹ binary and multinary coherent systems can be studied with unified arguments, through monotone binary coherent systems. These are binary coherent systems submitted to some monotone constraint and generalize the classic theory of free binary coherent systems. By considering the unified point of view thus obtained, this paper gives what is perhaps the most suggestive representation for multinary coherent systems, since this extends the definition of binary coherent systems in terms of series-parallel (parallel-series) structures. Then, this paper examines the special case of multinary systems that can be studied directly with the classic theory of free binary coherent systems. It thus enlarges and complements, in a shorter unified manner, the particular cases considered in earlier studies.     

Initial Segments in Rogers Semilattices of \Sigma _n^0 -Computable Numberings

S. Goncharov and S. Badaev showed that for , there exist infinite families whose Rogers semilattices contain ideals without minimal elements. In this connection, the question was posed as to whether there are examples of families that lack this property. We answer this question in the negative. It is proved that independently of a family chosen, the class of semilattices that are principal ideals of the Rogers semilattice of that family is rather wide: it includes both a factor lattice of the lattice of recursively enumerable sets modulo finite sets and a family of initial segments in the semilattice of -degrees generated by immune sets.