Novel halogenated cyclopentasilylene-2,4-dienes via DFT

In view of immense importance of silylenes and the fact that their properties undergo significant changes on substitution with halogens, here, we have used B3LYP/6-311++G** level of theory to access the effects of 1–4 halogens (X = F, Cl, Br, and I) on four unprecedented sets of cyclopentasilylene-2,4-dienes; with the following formulas: SiC₄H₃X ( 1 _X ), SiC₄H₂X₂ ( 2 _X ), SiC₄HX₃ ( 3 _X ), and SiC₄X₄ ( 4 _X ). In going down from F to I, the singlet (s)-triplet (t) energy gap (ΔE_s-t, a possible indication of stability), and band gap (ΔE_H-L) decrease while nucleophilicity (N), chemical potential (μ), and proton affinity (PA) increase. The overall order of N, μ, and PA for each X is 2 _X > 1 _X > 3 _X > 4 _X . Precedence of 2 _X over 1 _X is attributed to the symmetric cross conjugation in the former. The highest and lowest N are shown by 2 _I and 4 _F . The trend of divalent angle () for each X is 4 _X > 1 _X > 3 _X > 2 _X . The results show that in going from electron withdrawing groups (EWGs) to electron donating groups (EDGs), the ΔE_s-t and ΔE_H-L decrease while N, μ, and PA increase. Also, rather high N of our scrutinized silylenes may suggest new promising ligands in organometallic chemistry.     

Efficient Collocation Schemes for Singular Boundary Value Problems

We discuss an error estimation procedure for the global error of collocation schemes applied to solve singular boundary value problems with a singularity of the first kind. This a posteriori estimate of the global error was proposed by Stetter in 1978 and is based on the idea of Defect Correction, originally due to Zadunaisky. Here, we present a new, carefully designed modification of this error estimate which not only results in less computational work but also appears to perform satisfactorily for singular problems. We give a full analytical justification for the asymptotical correctness of the error estimate when it is applied to a general nonlinear regular problem. For the singular case, we are presently only able to provide computational evidence for the full convergence order, the related analysis is still work in progress. This global estimate is the basis for a grid selection routine in which the grid is modified with the aim to equidistribute the global error. This procedure yields meshes suitable for an efficient numerical solution. Most importantly, we observe that the grid is refined in a way reflecting only the behavior of the solution and remains unaffected by the unsmooth direction field close to the singular point.     

浅析二阶齐次线性变系数微分方程的一个可积类型

本文讨论了二阶齐次线性变系数微分方程的特殊形式，给出了这种微分方程的一个可积类型．     

A Reliability Analysis of Calculated Results for Odd-Even and Odd-Odd Nuclei in Relativistic Mean-Field Theory

We calculate the binding energies of Ni, Cu, Xe, Cs, Pt, Au, Np, Pu isotope chains using two interaction parameter sets NL-3 and NL-Z, and compared the relative errors of the even-even nuclei with those of odd-even nuclei and odd-odd nuclei. We find that the errors of binding energy of odd-even and odd-odd nuclei are not bigger than the one of even-even nuclei. The result shows that comparing with even-even nuclei, there is no systematic error and approximation in the calculations of the binding energy of odd-even and odd-odd nuclei with relativistic mean-field theory. In addition, the result is explained theoretically.     

On Quantum Team Games

Recently Liu and Simaan (2004) convex static multi-team classical games have been introduced. Here they are generalized to both nonconvex, dynamic and quantum games. Puu's incomplete information dynamical systems are modified and applied to Cournot team game. The replicator dynamics of the quantum prisoner's dilemma game is also studied.     

A primer on perfect simulation for spatial point processes

This primer provides a self-contained exposition of the case where spatial birth-and-death processes are used for perfect simulation of locally stable point processes. Particularly, a simple dominating coupling from the past (CFTP) algorithm and the CFTP algorithms introduced in [13], [14], and [5] are studied. Some empirical results for the algorithms are discussed. Received: 30 June 2002     

Collisional excitation of Na-Rydberg atoms

The scattering of heavy ion with a multilevel Rydberg atom in the presence of an electromagnetic field is studied. The interaction of Rydberg atom and the e.m field is explored using non-perturbative quasi-energy technique. Although the results are presented for selected excitations but in actual calculations we have included many levels of the atom. The effect of various parameters are shown on collisional excitation process. As an illustration detailed calculations are performed for the inelastic proton-Na Rydberg atom collision accompanied by the transfer of photons and the effects of dressing due to the field are considered. The emphasis of the present work is on collision induced transitions especially the case that involves change of orbital as well as principal quantum number. Received 26 December 2001 / Received in final form 8 April 2002 Published online 19 July 2002