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1.
Alexander Zeller 《Journal of organometallic chemistry》2006,691(21):4379-4385
The ethylene polymerization reaction of a neutral nickel catalyst was studied by DFT calculations at the Becke3LYP/6-31G(d) level of theory. As in related cases a β-agostic bond stabilizes the nickel alkyl ground states. Transition states for the insertion of the olefin show a distinct α-agostic interaction, which has not been observed for late metal polymerization catalysts before. An ethylene-alkyl complex was identified as the resting state of the reaction. The overall barrier height of the reaction amounts to 17.54 kcal/mol, which slightly increases to 17.60 kcal/mol for the polymerization of deuterated ethylene. Therefore, a small positive kinetic isotope effect (kH/kD = 1.09) can be calculated, which is caused by the α-agostic interaction in the transition state. A comparison to other late metal based polymerization systems reveals that the ethylene coordination step of highly active catalysts is significantly lower in energy compared to catalysts which are only moderately active. 相似文献
2.
We employ a first-principles plane wave method with the
relativistic analytic pseudopotential of Hartwigsen, Goedecker and Hutter
(HGH) scheme in the frame of DFT to calculate
the equilibrium lattice parameters and the thermodynamic properties of
AlB2 compound with hcp structure. The obtained lattice parameters are in
good agreement with the available experimental data and those calculated by
others. Through the quasi-harmonic Debye model, obtained successfully are
the dependences of the
normalized lattice parameters a/a0 and c/c0 on pressure P, the normalized
primitive cell volume V/V0 on pressure P, the variation of the thermal
expansion α with pressure P and temperature T, as well as the Debye
temperature \ThetaD and the heat capacity CV on pressure P and
temperature T. 相似文献
3.
Exact closed-form solutions are exhibited for the Hopf equation for stationary incompressible 3D Navier-Stokes flow, for the cases of homogeneous forced flow (including a solution with depleted nonlinearity) and inhomogeneous flow with arbitrary boundary conditions. This provides an exact method for computing two- and higher-point moments, given the mean flow. 相似文献
4.
5.
In this work we study nonnegativity and positivity of a discrete quadratic functional with separately varying endpoints. We introduce a notion of an interval coupled with 0, and hence, extend the notion of conjugate interval to 0 from the case of fixed to variable endpoint(s). We show that the nonnegativity of the discrete quadratic functional is equivalent to each of the following conditions: The nonexistence of intervals coupled with 0, the existence of a solution to Riccati matrix equation and its boundary conditions. Natural strengthening of each of these conditions yields a characterization of the positivity of the discrete quadratic functional. Since the quadratic functional under consideration could be a second variation of a discrete calculus of variations problem with varying endpoints, we apply our results to obtain necessary and sufficient optimality conditions for such problems. This paper generalizes our recent work in [R. Hilscher, V. Zeidan, Comput. Math. Appl., to appear], where the right endpoint is fixed. 相似文献
6.
Let T be a bounded linear operator on Hilbert space H, M an invariant subspace of T. If there exists another invariant subspace N of T such that H = M + N and M ∩ N = 0, then M is said to be a completely reduced subspace of T. If T has a nontrivial completely reduced subspace, then T is said to be completely reducible; otherwise T is said to be completely irreducible. In the present paper we briefly sum up works on completely irreducible operators that
have been done by the Functional Analysis Seminar of Jilin University in the past ten years and more.
The paper contains four sections. In section 1 the background of completely irreducible operators is given in detail. Section
2 shows which operator in some well-known classes of operators, for example, weighted shifts, Toeplitz operators, etc., is
completely irreducible. In section 3 it is proved that every bounded linear operator on the Hilbert space can be approximated
by the finite direct sum of completely irreducible operators. It is clear that a completely irreducible operator is a rather
suitable analogue of Jordan blocks in L(H), the set of all bounded linear operators on Hilbert space H. In section 4 several questions concerning completely irreducible operators are discussed and it is shown that some properties
of completely irreducible operators are different from properties of unicellular operators.
__________
Translated from Acta Sci. Nat. Univ. Jilin, 1992, (4): 20–29 相似文献
7.
Modulo some natural generalizations to noncompact spaces, we show in this Letter that Moyal planes are nonunital spectral triples in the sense of Connes. The action functional of these triples is computed, and we obtain the expected result, i.e. the noncommutative Yang–Mills action associated with the Moyal product. In particular, we show that Moyal gauge theory naturally fits into the rigorous framework of noncommutative geometry. 相似文献
8.
We investigate the dynamics of the Λ system driven by two resonant laser fields in presence of dissipation for coupling strengths where the rotating‐wave approximation starts to break down. This regime is characterised by Rabi frequencies being approximately equal or smaller than the field frequencies. A systematic procedure to obtain an expansion for the solution of the Bloch evolution equations of the system is presented. The lowest contribution results to be the well‐known rotating‐wave approximation. The method is based on a semi‐classical treatment of the problem, and its predictions are interpreted fully quantum mechanically. The theory is illustrated by a detailed study of the disappearance of coherent population trapping as the intensities of the fields increase. 相似文献
9.
Arnon Arazi Eshel Ben-Jacob Uri Yechiali 《Mathematical Methods of Operations Research》2005,62(3):453-466
We consider a Jackson-type network comprised of two queues having state-dependent service rates, in which the queue lengths
evolve periodically, exhibiting noisy cycles. To reduce this noise a certain heuristic, utilizing regions in the phase space
in which the system behaves almost deterministically, is applied. Using this heuristic, we show that in order to decrease
the probability of a customers overflow in one of the queues in the network, the server in that same queue – contrary to intuition
– should be shut down for a short period of time. Further noise reduction is obtained if the server in the second queue is
briefly shut down as well, when certain conditions hold. 相似文献
10.
使用Monte Carlo模拟的方法得出了随机粗糙表面,在Kirchhoff近似的基础上,利用数值分析的方法分析了一维随机粗糙表面的散射特征,得出了一维随机粗糙表面散射分布曲线,我们还考虑了遮蔽效应的影响,并且讨论了Kirchhoff近似的有效性。 相似文献