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.     

Equilibrium theory of two-dimensional simple liquids

Using the Wigner-Kirkwood expansion and bare Lennard-Jones (LJ) (12-6) potential, an effectiveLJ potential is derived, which includes the quantum effects through the expressions of the effective diameter∂(T, λ) and well-depth (T, λ). We use theWCA perturbation theory to calculate the free energy and pressure for theLJ and effectiveLJ potentials. Simple analytic expressions are given for the reference system and the first order correction calculated. The results are quite good at high density. The quantum effects on the free energy and pressure are also discussed.     

An application of correlation energy density functionals to atoms and molecules

Four density functionals — including that recently introduced by Perdew ((1986) Phys Rev B33: 8822)—are tested for first-row atoms, hydrides and dimers. Calculated contributions of the correlation energy to the ionization potentials and electron affinities of atoms and to the dissociation energies of molecules are compared with empirical values which were reevaluated for this purpose. An improvement over Hartree-Fock is found in all cases if the self-interaction or the gradient correction are included in the density functional, although there is a rather large variation in the accuracy of the predictions.     

PHOTOEMISSION WITHIN AND BEYOND THE ONE-STEP MODEL

Photoemission in the vacuum ultraviolet photon regime has proved to be an effective tool for the investigation of valence band surface electronic structure. The interpretation cannot be exclusively confined to the valence bands but has to consider cross sections with realistic final states consistently designed within the one-step model. Therefore especially in the surface sensitive photoemission, several effects hide the final goal of deducing the energetic and wavefunction structure together with microscopic potential parameters through a convincing agreement of calculated with measured spectra. The final states band structure is much less well understood than the valence band structure under consideration. The optical potential, which controls the surface sensitivity through the underlying damping mechanisms, widely relies on empirical assumptions. Furthermore, the photon field is not only strongly influenced but in the vicinity of the plasma frequency also deteriorated by the electronic response. In view of high resolution spectroscopy the accuracy of the data interpretation is affected, and in fact, band-mapping methods are no longer valid. Examples of recent calculations to account for these effects are reviewed.     

O(~1D)+Si(CH_3)_3Cl反应生成振动激发的OH(υ≤5)

实验光谱学和理论计算都发现,“重原子”能隔离分子中的某些振动能景,如SiH_4中Si—H振动泛频的“局域模”.Roger 等在研究F 原子与M(CH_2CH=CH_2)_4(M=Sn,Ge)的反应中,发现了Sn,Ge 对过剩能量转移到其它部分有强烈的阻碍作用(在中间态的寿命时间内).最近,在研究O(~1D)+M(CH_3)_4生成OH(v)反应中,观测到类似的现象.M=C 时,Lutz 用激光诱导荧光方法检测OH 的振动分布,振动是冷的,v=1与v=0的布居比为0.05,     

The use of 1H NMR microscopy to study proton-exchange membrane fuel cells.

To understand proton-exchange membrane fuel cells (PEMFCs) better, researchers have used several techniques to visualize their internal operation. This Concept outlines the advantages of using 1H NMR microscopy, that is, magnetic resonance imaging, to monitor the distribution of water in a working PEMFC. We describe what a PEMFC is, how it operates, and why monitoring water distribution in a fuel cell is important. We will focus on our experience in constructing PEMFCs, and demonstrate how 1H NMR microscopy is used to observe the water distribution throughout an operating hydrogen PEMFC. Research in this area is briefly reviewed, followed by some comments regarding challenges and anticipated future developments.     

Li+与线性碳链HC2n-体系相互作用的理论研究

应用密度泛函理论(DFT)和多体微扰理论(MP2),对Li 与线性碳链HC2n-形成的体系HC2nLi(n=1~8,C∞v)的平衡几何构型、谐振动频率、第一绝热电离能和结合能进行了研究并计算了HC2n-与Li 之间相互作用的势能曲线。计算结果表明,Li 可与线性碳链HC2n-形成稳定的化合物HC2nLi;化合物的电离能和结合能与体系大小n之间存在非线性关系。基于计算结果,得到了体系的绝热电离能和结合能与体系大小n的解析表达式。     

一种新型稀土配合物Eu(TTA)2(N-HPA)Phen的发光特性研究

合成了一种新的含有3个配体的稀土配合物Eu（TTA）2（N-HPA）Phen（TTA-噻吩甲酰基三氟丙酮，N—HPA=N-苯基邻氨基苯甲酸，phen=邻菲咯啉）。将稀土配合物作为掺杂物与基质PVK按照不同质量比混合共溶，旋涂成膜。通过荧光光谱，分析了薄膜的发光特性，并将其应用于有机电致发光。研究了PVK和Eu（TTA）2（N—HPA）Phen之间的能量传递，并且制备了发光层为PVK：Eu（TTA）2（N—HPA）Phen，结构为ITO／PVK：Eu（TrA）2（N—HPA）Phen／BCP／Alq3／Al的多层器件，发现改变PVK和稀土配合物的掺杂比，可以不同程度地抑制PVK的发光，最终得到纯的Eu^3＋的红色发光。实验结果证明，在PVK：Eu（TTA）2（N—HPA）Phen=5：1的质量比下，从PVK到稀土配合物之间存在充分的能量传递。     

Intramolecular proton transfer induced by divalent alkali earth metal cation in the gas state

Interactions between divalent alkali earth metal (DAEM) ions M (M?Be, Mg, Ca, Sr, Ba) and the second stable glycine conformer in the gas phase, which can transfer into the ground‐state glycine‐M²⁺ (except the glycine–Be²⁺) among each corresponding isomers when these divalent metal ions are bound, are studied at the hybrid three‐parameter B3LYP level with three different basis sets. Proton transfers from the hydroxyl to the amino nitrogen of the glycine without energy barriers have been first observed in the gas phase in these glycine–M²⁺ systems. The interaction between the glycine and these DAEM ions except beryllium and magnesium ion only create an amino hydrogen pointing to the original hydroxyl due to their weaker interaction relative to those divalent transition metal (DTM) ion‐bound glycine derivatives, being obviously different from that between the glycine and DTM ions, in which two amino hydrogens point to the original hydroxyl oxygen when these metal‐chelated glycine derivatives are produced. The interaction energy between the glycine and divalent magnesium would be the boundary of one or two amino hydrogens pointing to the hydrogyl oxygen, i.e., the ?170.3 kcal/mol of binding energy is a critical point. Similar intramolecular proton transfer has also been predicted for those DTM ion‐chelated glycine systems; however, that in the gas state has not been observed in the monovalent metal ion‐coordinated glycine systems. The binding energy between some monovalent TM ion and the glycine is similar to that of the glycine–Ba²⁺, which has the lowest binding strength among these DAEM–ion chelated glycine complexes. The difference among them only lies in the larger electrostatic and polarized effects in the latter, which favor the stability of the zwitterionic glycine form in the gas phase. According to these observations, we predict that the zwitterionic glycine would exist in the field of two positive charges in the gas phase. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 94: 205–214, 2003     

Chemical equilibrium model for the thermodynamic properties of mixed aqueous micellar systems: Application to thermodynamic functions of transfer

Mixed micelles can be formed in water between various pairs of hydrophobic solutes such as surfactants, alcohols and hydrocarbons. These systems can often be studied through the thermodynamic functions of transfer of one of the solutes, usually kept near infinite dilution, from water to an aqueous solution of the other solute. When mixed micelles are formed, these functions change significantly, and often go through extrema, in the region where the binary system micellizes or undergoes some microphase transition.Three main effects are responsible for the observed trends: pair-wise interactions between both solutes in the monomeric form, a distribution of the reference solute between the aqueous and micellar phases and a shift in the monomer-micelle equilibrium in the vicinity of the reference solute. Simple equations can be derived for these three effects which can account for the sign and magnitude of the observed trends using parameters which are derived for the most part from the two binary systems.