Explicit Convergence Rates of the Embedded M/G/1 Queue

This paper investigates the explicit convergence rates to the stationary distribution π of the embedded M/G/1 queue; specifically, for suitable rate functions r（n） which may be polynomial with r（n） = n^l, l 〉 0 or geometric with r（n） = α^n, a 〉 1 and ＂moments＂ f ≥ 1, we find the conditions under which Σ∞n=0 r（n）｜｜P^n（i,·） - π（·）｜｜f ≤ M（i） for all i ∈ E. For the polynomial case, the explicit bounds on M（i） are given in terms of both ＂drift functions＂ and behavior of the first hitting time on the state O; and for the geometric case, the largest geometric convergence rate α＊ is obtained.     

Non-linear scission/recombination kinetics of living polymerization

Living polymers are formed by reversible association of primary units (unimers). Generally the chain statistical weight involves a factor σ < 1 suppressing short chains in comparison with free unimers. Living polymerization is a sharp thermodynamic transition for σ ≪ 1 which is typically the case. We show that this sharpness has an important effect on the kinetics of living polymerization (one-dimensional association). The kinetic model involves i) the unimer activation step (a transition to an assembly-competent state); ii) the scission/recombination processes providing growth of polymer chains and relaxation of their length distribution. Analyzing the polymerization with no chains but unimers at t = 0 , with initial concentration of unimers M ≳ M ^* (M^* is the critical polymerization concentration), we determine the time evolution of the chain length distribution and find that: 1) for M ^* ≪ M ≪ M ^*/σ the kinetics is characterized by 5 distinct time stages demarcated by 4 characteristic times t₁, t₂, t₃ and t^*; 2) there are transient regimes (t ₁ ≲ t ≲ t ₃) when the molecular-weight distribution is strongly non-exponential; 3) the chain scissions are negligible at times shorter than t₂. The chain growth is auto-accelerated for t ₁ ≲ t ≲ t ₂ : the cut-off chain length (= polymerization degree 〈n〉_w N ₁ ∝ t ² in this regime. 4) For t ₂ < t < t ₃ the length distribution is characterized by essentially 2 non-linear modes; the shorter cut-off length N₁ is decreasing with time in this regime, while the length scale N₂ of the second mode is increasing. (5) The terminal relaxation time of the polymer length distribution, t^*, shows a sharp maximum in the vicinity of M^*; the effective exponent is as high as ∼ σ^-1/3 just above M^*.     

The relationship between absorption coefficient and temperature and their effect on the atmospheric cooling rate

Several approaches are considered to determine the temperature effect on the absorption coefficient within a correlated k-distribution method. Taking in the 610- region for example, the absorption coefficients and atmospheric cooling rates calculated using these approaches are compared with line-by-line integration. It is emphasized in this paper by numerical calculation that the effect of pressure on absorption coefficient is related to temperature and vise versa; the larger the pressure, the larger the effect of temperature on absorption coefficient. Results show that the temperature effect must be considered in radiative calculations although its effect on the absorption coefficient is much smaller than that of pressure.     

中英化学教材“化学反应速率”内容比较研究

“化学反应速率”综合体现了微粒观、实验观及科学本质观等化学基本观念,是提高学生科学素养的重要载体。从内容选取、内容编排与内容呈现3个方面对英国索尔特高级化学课程教材与国内化学教材中“化学反应速率”相关内容的编写进行比较,并简要阐述几点对化学教材编写和化学教学的启示。     

Peeling behavior of a viscoelastic thin-film on a rigid substrate

In order to study the adhesion mechanism of a viscoelastic thin-film on a substrate, peeling experiment of a viscoelastic polyvinylchloride (PVC) thin-film on a rigid substrate (glass) is carried out. The effects of peeling rate, peeling angle, film thickness, surface roughness and the interfacial adhesive on the peel-off force are considered. It is found that both the viscoelastic properties of the film and the interfacial adhesive contribute to the rate-dependent peel-off force. For a fixed peeling rate, the peel-off force decreases with the increasing peeling angle. Increasing film thickness or substrate roughness leads to an increase of the peel-off force. Viscoelastic energy release rate in the present experiment can be further predicted by adopting a recently published theoretical model. It is shown that the energy release rate increases with the increase of peeling rates or peeling angles. The results in the present paper should be helpful for understanding the adhesion mechanism of a viscoelastic thin-film.     

Temperature dependence of the rate constant of ionic analogs of H + H2 → H2 + H reaction by quantum instanton method

Rate constant ratios k(T)/k(1,500K) for two symmetrical reactions H^? + H₂ → H₂ + H^? and H⁺ + H₂ → H₂ + H⁺ are reported. Direct method based on quantum instanton approximation for evaluation of the temperature dependence of the quantum‐mechanical reaction rate constant is used. Implementation of the theory involves thermodynamic integration and path integral Monte Carlo method. Results of anionic case shows resemblance to neutral case, whereas cationic case is significantly different and below 1,000K rate constant shows strong deviation form linearity of Arrhenius plot due to high activation barrier. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012     

Rf‐GDOES analysis of composite metal/ceramic electroplated coatings with nano‐ to microceramic particles' size: issues in plasma sputtering of Ni/micro‐SiC coatings

Ni matrix composite coatings reinforced with nano‐ and microceramic particles were analyzed by radio frequency glow discharge optical emission spectrometry (Rf‐GDOES). An interesting phenomenon related to the sputtering and excitation modes of this technique was observed. During plasma sputtering with Rf‐GDOES, the micro‐SiC particles were detached from metal matrix and did not contribute to the analytical signals. The same was not found in composite coatings containing nanoceramic particles. This anomalous behavior was confirmed by atomic force microscopy (AFM) investigation and scanning electron microscope (SEM) observations into Rf‐GDOES craters that showed the presence of residual non‐sputtered microparticles. Various attempts were done in order to minimize this problem, mainly by varying the analysis parameters of the used instrumentation, but without any relevant success. Some suggestions were then proposed for explaining the observed phenomenon, moreover possible solutions (e.g. by using a strong magnetic field or changing plasma gas to be more energetic) are discussed. Copyright © 2011 John Wiley & Sons, Ltd.     

An extension of the grid empowered molecular simulator to quantum reactive scattering

Within the activities of the D37 COST Action, we have further developed the quantum dynamics framework of the grid empowered molecular simulator (GEMS) implemented on the segment of the European grid available to the COMPCHEM (computational chemistry) virtual organization. GEMS does now include in a full ab initio approach, the evaluation of the detailed quantum (both time dependent and time independent) dynamics of small systems starting from the calculation of the electronic structure properties as well as the direct calculation of thermalized properties. Illustrative, full dimensional applications of the extended simulator to the H + H(2) , N + N(2) , and O + O(2) systems are presented.     

Theoretical study on the reaction CX3 + SiH(CH3)3 (X = H, F)

Theoretical investigations are carried out on the multiple-channel reactions, CH(3) + SiH(CH(3))(3) → products and CF(3) + SiH(CH(3))(3) → products. The minimum energy paths (MEP) are calculated at the MP2/6-311 + G(d,p) level, and energetic information is further refined by the MC-QCISD (single point) method. The rate constants for major reaction channels are calculated by the canonical variational transition state theory (CVT) with small-curvature tunneling (SCT) correction over the temperature range 200-1500 K. The theoretical rate constants are in good agreement with the available experimental data and are found to be k(1a)(T) = 1.93 × 10(-24) T(3.15) exp(-1214.59/T) and k(2a)(T) = 1.33 × 10(-25) T(4.13) exp(-397.94/T) (in unit of cm(3) molecule(-1) s(-1)). Our calculations indicate that hydrogen abstraction channel from SiH group is the major channel due to the smaller barrier height among five channels considered.