气相中Fe+催化CO与N2O循环反应的理论计算研究

采用密度泛函UB3 LYP/6-311+ G(2d)方法研究了Fe+在基态和激发态与CO与N2O反应的反应机理.全参数优化了反应势能面上各驻点的几何构型,用频率分析方法和内禀反应坐标(IRC)方法对过渡态进行了验证,并用UB3LYP/6-311++G(3df,3pd)、单点垂直激发等方法分别进行各驻点单点能校正,四重态和六重态反应势能面交叉点CP确定,计算结果表明,该反应为两步反应,且反应机理都为插入一消去反应,势能面上的两个交叉点能够有效降低反应的活化能,这在动力学和热力学上都是有利的.     

Nearly light cycles in embedded graphs and crossing‐critical graphs

We find a lower bound for the proportion of face boundaries of an embedded graph that are nearly light (that is, they have bounded length and at most one vertex of large degree). As an application, we show that every sufficiently large k‐crossing‐critical graph has crossing number at most 2k + 23. © 2006 Wiley Periodicals, Inc. J Graph Theory 53: 151–156, 2006     

Factorization Representations in the Boundary Crossing Problems for Random Walks on a Markov Chain

Let τ be some stopping time for a random walk S _n defined on transitions of a finite Markov chain and let τ(t) be the first passage time across the level t which occurs after τ. We prove a theorem that establishes a connection between the dual Laplace-Stieltjes transforms of the joint distributions of (τ, S _τ) and (τ(t), S _τ(t)). This result applies to the study of the number of crossings of a strip by sample paths of a random walk.Original Russian Text Copyright © 2005 Lotov V. I. and Orlova N. G.The authors were partially supported by the Russian Foundation for Basic Research (Grant 05-01-00810) and the Grant Council of the President of the Russian Federation (Grant NSh-2139.2003.1).__________Translated from Sibirskii Matematicheskii Zhurnal, Vol. 46, No. 4, pp. 833–840, July–August, 2005.     

Electronic excitation and singlet-triplet coupling in uracil tautomers and uracil-water complexes

Electronic spectra of uracil in its diketo (lactam) form and five enol (lactim) tautomeric forms have been investigated by means of combined density functional and configuration interaction methods. We have simulated the effects of hydrogen bonding with a protic solvent by recomputing the spectrum of uracil in the presence of two, four, or six water molecules. Geometries of the electronic ground state and several low-lying excited states have been optimized. Spin-orbit coupling has been determined for correlated wavefunctions employing a non-empirical spin-orbit mean-field approach. In accord with experiment, we find the diketo tautomer to be the most stable one. The calculations confirm that the first absorption band arises from the ¹( π↦π^*) S ₀↦S ₂ excitation. The experimentally observed vibrational structure in this band originates from a breathing mode of the six ring. Complexation with water molecules is seen to cause a significant blue shift of n↦π^* excitations while leaving π↦π^* excitations nearly uninfluenced. Computed radiative lifetimes are presented for the experimentally known weak phosphorescence from the π↦π^* excited T₁ state. Among the uracil lactim tautomers, one is particularly interesting from a spectroscopic point of view. In this tautomer, the π↦π^* excitation gives rise to the S₁ state. Received 18 February 2002 / Received in final form 5 June 2002 Published online 13 September 2002     

Log Structures on Generalized Semi-Stable Varieties

In this paper, a class of morphisms which have a kind of singularity weaker than normal crossing is considered. We construct the obstruction such that the so-called semi-stable log structures exists if and only if the obstruction vanishes. In the case of no power, if the obstruction vanishes, then the semi-stable log structure is unique up to a unique isomorphism. So we obtain a kind of canonical structure on this family of morphisms.     

基于GIS的河道、蓄滞洪区洪水演进动态可视化仿真研究

结合地理信息系统(GIS)技术和三维仿真图示技术,探讨了基于GIS的河道、蓄滞洪区洪水演进可视化仿真技术原理与方法,分析了洪水演进可视化模型的建立过程,设计出河道、蓄滞洪区洪水演进系统的总体结构及开发模式,并介绍了系统具体功能的实现.本仿真模型在实例中得到了成功的应用,可为防洪减灾决策提供快捷、直观形象的信息支持.     

Modelling groundwater changes due to fluctuating dam discharge

In this contribution, two numerical methods are used to predict the free surface changes in a sand bar due to fluctuations in river stage. One is a fixed-mesh, finite-element seepage formulation including Biot's consolidation theory, and the other is a boundary element method solution of the Laplace equation. Both models give overall predictions that are in good agreement with field data recorded at an instrumented sand bar in the Colorado River subjected to stage fluctuations from operation of the Glen Canyon Dam. The boundary element method appears to offer significant advantage in data preparation and computational times over the finite-element method for the problem studied in this paper.     

Modeling of water-drain and salt-transfer processes on swamped lands

Hydrodynamic and hydraulic models of water drain on swamped lands are proposed, which describe the processes of filtration and surface drain with different degrees of detail and accuracy. Based on the models of salt transfer by interacting filtration and riverbed flows, the issues of modeling the quality of subsoil and surface waters are considered.Translated from Prikladnaya Mekhanika i Tekhnicheskaya Fizika, Vol. 46, No. 1, pp. 96–105, January–February, 2005     

The distribution of values of trigonometric sums with linearly independent frequencies: Kac's problem revisited

The average frequency with which a trigonometric sum having linearly independent frequencies achieves a given value in a specified time interval was solved by Kac in the form of a double integral. In the present paper, Kac's solution is generalized by allowing the amplitudes of the sinusoidal terms to be statistically independent random variables possessing compact probability density functions. The average frequency is expressed as a Fourier cosine series. Representative numerical calculations are shown. The asymptotic form of the average frequency is also discussed.     

Ribbon-moves for 2-knots with 1-handles attached and Khovanov-Jacobsson numbers

We prove that a crossing change along a double point circle on a -knot is realized by ribbon-moves for a knotted torus obtained from the -knot by attaching a -handle. It follows that any -knots for which the crossing change is an unknotting operation, such as ribbon -knots and twist-spun knots, have trivial Khovanov-Jacobsson number.