Enhancement of activated decay of metastable states by resonant pumping

We consider the effect of a high-frequency pumping cost on the escape rate of a classical underdamped Brownian particle out of a deep potential well. The energy dependence of the oscillation frequency(E) is assumed to be weak on the scale of thermal energy,_E(0)T(0)T/V₀ (0)[_E(0) is the derivative of(E) atE= 0,V ₀ is the barrier height,V ₀ T]. The quadratic-in- contribution to the decay rate is calculated in two different regimes: (1) for the case of resonance of the pumping frequency with the nth harmonic of the internal motion at an energye, when = n(e); (2) for a rollout region of the basic resonance near the bottom of the potential well, when ¦-(0)¦ and is the damping coefficient. In the latter case the absorption spectrum and the enhancement of the decay rate are calculated as functions of two reduced parameters, the anharmonicity of the potential,v _E (0)T/, and the resonance mismatch, [ —(0)]/. It is shown that the effect of the pumping increases with diminishing ¦v¦ and at small v is proportional tov ^–1. In this regime, the dependence on is stepwise: the pumping contribution is large for v > 0 and small for v < 0. In the frame of our theory, the decay rate is invariant against the simultaneous alternation of the signs of andv. The spectrum of the energy absorption has the standard Lorentzian shape in the absence of anharmonicity,v=0, and with increasing of ¦v¦ shifts and widens retaining its bell-shape form.     

Reversible dynamics and the macroscopic rate law for a solvable Kolmogorov system: The three bakers' reaction

We investigate a piecewise linear (area-preserving) mapT describing two coupled baker transformations on two squares, with coupling parameter 0c1. The resulting dynamical system is Kolmogorov for anyc0. For rational values ofc, we construct a generating partition on whichT induces a Markov chain. This Markov structure is used to discuss the decay of correlation functions: exponential decay is found for a class of functions related to the partition. Explicit results are given forc=2^–n. The macroscopic analog of our model is a leaking process between two (badly) stirred containers: according to the Markov analysis, the corresponding progress variable decays exponentially, but the rate coefficients characterizing this decay are not those determined from the one-way flux across the cell boundary. The validity of the macroscopic rate law is discussed.     

微波辅助-光催化降解氯酚的QSPR研究

本文运用PM3算法计算得到氯酚(CPs)的分子结构参数,并结合光解速率进行PLS分析,建立了速率与量子化参数之间的关系模型,模型的Q2cum分别为0.8776和0.9545(>0.5),具有良好的预测能力。研究结果表明,参数Ehomo、Elumo Ehomo、Elumo、N、Mw、Elumo-Ehomo、(Elumo-Ehomo)2是决定CPs光解速率的主要因素;CPs的光解速率随Ehomo、Elumo Ehomo、Elumo、Elumo-Ehomo、(Elumo-Ehomo)2的增大而增大,随N、Mw的增大而减小。     

Fluorescence decay and quenching of pyrene labeled on sulfonate polyelectrolytes in salt-free aqueous solutions

Fluorescence decay and quenching of pyrene labels on copolymers of 2-acrylamido-2-methylpropanesulphonic acid (AMPS) and N,N-dimethylacrylamide were observed in dilute salt-free aqueous solutions as a function of the mole fraction F_AMPS of AMPS from 0 to 0.896. Monoexponential decay was found for the samples of F_AMPS<0.35 and biexponential decay for the samples of F_AMPS>0.35. The fast decay component is 80%, and the averaged lifetime 〈τ〉 and lifetime τ₁ of the fast decay is decreased with increasing F_AMPS. Quenching efficiency of Cu²⁺, I⁻, CH₃NO₂, and dinitrobenzene to the pyrene label was investigated in the framework of Stern-Volmer plot. With increasing F_AMPS the quenching efficiency of Cu²⁺ is increased while that of I⁻ decreased. For the neutral quenchers, the quenching rate constant k_q increases when F_AMPS<0.449 then decreases, showing a decline of accessibility to the pyrene label. These results were interpreted consistently with the counterion condensation concept, where condensed counterions caused the polyelectrolyte chains to aggregate. The existence of less-polar “temporal aggregated domain” in highly charged polyelectrolytes appears to lead to the slower decay and lower accessibility of the pyrene labels.     

停留—催化反应速差动力学法同时测定Fe,Mo

根据Ｆｅ（Ⅲ）、Ｍｏ（Ⅵ）对Ｈ２Ｏ２氧化邻氨基酚的催化反应速率不同，结合流动注射停留技术，建立了同时测定Ｆｅ（Ⅲ）、Ｍｏ（Ⅵ）的速差动力学分光光度法．测定铁和钼的线性范围分别为０．１～２．５μｇ／ｍＬ和０．５～１５μｇ／ｍＬ．除Ｗ（Ⅵ）的允许量较小外，其它离子不干扰测定．用本法测定了合成样液中铁和钼含量，结果满意．     

A modified simplex method for multifactor optimization of selectivity in gas chromatography

A computer-assisted advanced simplex method is presented for the simultaneous optimization of multifactor ( stationary phase loading, carrier gas flow rate and column temperature ) for separation of ten compounds in gas chromatography. A three factors factorial design was used. The method was based on a special polynomial established from fifteen preliminary runs, using resolution as the selection criterion, with connection to a general simplex method. Excellent agreement is found between the predicted data and the experimental results, and most of experiments required in the general simplex method can be omitted.     

烯烃加成反应活性与烷基极化效应的关系

烯烃的自由基加成和亲电加成速率受不同的因素控制.对于仅仅含烷基取代的简单烯烃:(1)与OH自由基加成速率-log kOH可由π键上烷基极化效应指数的几何平均值GMPEIπ关联:-log kOH=a bGMPEIπ c(GMPEIπ)2; (2)与亲电试剂加成速率log k可由π键两端碳原子所连基团极化效应指数PEI(L)和PEI(S)关联:log k=a bPEI(L) cPEI(S),其中的PEI(L)和PEI(S)分别表示极化效应较大和较小的一端.     

STRUCTRE AND PROPERTIES OF COMPOSITE Ni/HARD CARBON FILMS PREPARED BY PLASMA DEPOSITION

IntroductionHardcarbonfilmsprcparcdb}'vari0usplasmaprocesscsareofc0nsidcrablcinterestbccauscofthcirunusualmcchanical-opticalandelcctricalpropertiesll~3l.Rccently,ithasReceive(IJl111c5,l9`)5;,.`,1iis()tI1ie)\tioII,1'ceil'edJtl1)'l4,l995*'I11isprojectiss[1pportcdh}tl1cNatiol1a1Nat[lntlScicl1ccI`()ul1dati()l1ofCl1il1aal1dtl1eI,aboraton'ofSolidI,ubricati()l1,l.al1/l10ulnstitutcofCl1cn1icalPh\'sics,111cChincscAcadcl11\'ofScicnccs.benfoundthattheinc0rporati0nofmetaIintocarbonfilmscangrcatl}'…