Partially isometric dilations of noncommuting -tuples of operators

Given a row contraction of operators on a Hilbert space and a family of projections on the space that stabilizes the operators, we show there is a unique minimal joint dilation to a row contraction of partial isometries that satisfy natural relations. For a fixed row contraction the set of all dilations forms a partially ordered set with a largest and smallest element. A key technical device in our analysis is a connection with directed graphs. We use a Wold decomposition for partial isometries to describe the models for these dilations, and we discuss how the basic properties of a dilation depend on the row contraction.

     

最大无关组的判定定理及其它

本文给出了一个判定最大无关组的充要性定理及其证明．同时对用矩阵的行变换求最大无关组这一问题进行了点滴分析并介绍了一个解齐次线性方程组的简便方法。     

赋权矩阵及其性质

本文给出了以S为行权和向量的权矩阵类T_＋(S)中每个权矩阵都可逆的一个充要条件．     

Second row transition metal mixed hydride-halide triatomic molecules

Summary The ground state structures and bond energies have been obtained for the triatomic MHX systems where M is the entire sequence of second row transition metal atoms and X is a halide. The most interesting results of this study appear when these systems are compared to the triatomic MH₂ and MX₂ systems. It turns out that the structure of the MHX systems are quite similar to the corresponding MH₂ systems in general. Most of the MHX systems to the right thus have bent low-spin ground states, indicating large covalent contributions to the bonding. RuHX is a special case and has a high-spin linear ground state. For the systems to the left ionicity dominates the bonding. An important result, with implications for halide ligand effects on carbonyl and olefin insertion into M-H and M-R bonds, is that the M-H bonds for the systems to the right have a different character and are significantly weaker for the MHX than for the MH₂ systems. A similar effect is noted when the M-Cl bond strengths of MCl₂ are compared to the ones in MHCl. Both these effects can be explained by a more cationic metal with mores ⁰-state character when halide ligands are present.     

Stress Distribution in an Elastic Body with a Periodically Curved Row of Fibers

Within the framework of a piecewise homogeneous body model, with the use of exact three-dimensional equations of elasticity theory for anisotropic bodies, a method is developed for investigating the stress distribution in an infinite elastic matrix containing a periodically curved row of cophasal fibers. It is assumed that fiber materials are the same and fiber midlines lie in the same plane. The self-balanced stresses arising in the interphase in uniaxial loading the composite along the fibers are investigated. The influences of problem parameters on these stresses are analyzed. The corresponding numerical results are presented.     

布尔矩阵维数的缺断区间(英)

本文证明了n维布尔矩阵维数的一个新的缺断区间为这一结果扩充了一些已知的结论．     

Gaussian basis sets for calculation of spin densities in first-row atoms

Summary The suitability of Gaussian basis sets for ab initio calculation of Fermi contact spin densities is established by application to the prototype first-row atoms B-F having open shell p electrons. Small multiconfiguration self-consistent-field wave functions are used to describe relevant spin and orbital polarization effects. Basis sets are evaluated by comparing the results to highly precise numerical grid calculations previously carried out with the same wave function models. It is found that modest contracted Gaussian basis sets developed primarily for Hartree-Fock calculations can give semiquantitative results if augmented by diffuse functions and if further uncontracted in the outer core-inner valence region.     

Contracted polarization functions for B to Ar

Using optimal exponents for B through Ne given by Dunning and those for Al through Ar by Woon and Dunning, d-type contracted polarization functions (2d/1d), (3d/1d), and (3d/2d) are generated from natural orbitals of atomic single and double excitation configuration interaction (SDCI) calculations, where the numbers before and after the slash are those of the primitive and contracted Gaussian type functions. The resulting contracted functions are tested on N₂ and P₂ molecules by self-consistent field and SDCI calculations, which clarify characteristics of the present polarization functions. Received: 5 June 1997 / Accepted: 20 August 1997     

The activation of the C-H bond in acetylene by second row transition metal atoms

Summary The C-H activation reaction of acetylene by second row transition metal atoms has been studied including electron correlation of all valence electrons. Binding energies have been computed for both -coordinated complexes and C-H insertion products. It is found that for most atoms the -coordinated complexes are thermodynamically favoured, just as in the case for the corresponding ethylene reaction. The barrier height for the C-H insertion increases from acetylene to ethylene and to methane. This is in line with the experimental finding that there should be an inverse relation between C-H bond strengths and the difficulty to activate these bonds. To explain the detailed differences between the C-H activation of acetylene and ethylene, the interaction with two, rather than one, - and *-orbitals for acetylene is of key importance. The barrier height for the acetylene reaction increases significantly between niobium and molybdenum going to the right in the periodic table, just as for all oxidative addition reactions previously studied. The origin of this increase is that noibium has one empty 4d-orbital but for molybdenum all 4d-orbitals are occupied. Rhodium has the lowest barrier for C-H activation for all systems studied.     

Implementation of a general multireference configuration interaction procedure with analytic gradients in a semiempirical context using the graphical unitary group approach

The graphical unitary group approach has been applied in an efficient implementation of a general multireference configuration interaction (MRCI) method for use with small active molecular orbital spaces in a semiempirical framework. Gradients can be computed analytically for molecular orbitals from a closed-shell or a half-electron open-shell Hartree-Fock calculation. CPU times for single point energy and gradient calculations are reported. The code allows MRCI geometry optimizations of large molecules, as illustrated for the singlet ground state and the four lowest triplet states of fullerene C(76).