Photoinduced Electron Transfer From Carbazole to Halomethanes in a Gas Phase

Intermolecular photoinduced electron transfer (PET) in a gas phase was studied using carbazole vapor fluorescence quenching by halomethanes (CHCl₃, CH₂Br₂, CCl₄, CHBr₃). The fluorescence quenching rate constants k _q changing from 2.3·10⁵ sec^–1·torr^–1 in mixtures with CHCl₃ to 4.6·10⁶ sec^–1·torr^–1 in mixtures with CHBr₃ at a constant temperature of 403 K were estimated. The dependence of the carbazole fluorescence decay rates in the presence of halomethanes on the free energy change G during transfer of the electron from carbazole to halomethanes is considered. It is suggested to take into account the influence of the vibrational energy of the carbazole molecule E _vib and its temperature changes in estimation of the G values. The differences between PET in the gas and liquid phases were analyzed. It is found that for mixtures with CCl₄ and CHBr₃ the negative temperature dependence of k _q is observed, when the decay rates and efficiencies of the intermolecular PET decreased with temperature increase in the range 403–573 K, i.e. these mixtures the electron transfer is not a barrier-restricted process.     

Analysis of Two-Dimensional Optical Fields Using an Additional Shift

A solution to the phase problem in optics is considered within the context of registration and analysis of two-dimensional stationary optical fields transformed by the object under study or fields forming an image. To obtain information on amplitude and phase distributions of the light field analyzed, a method of registration of two intensity distributions is used. The first distribution corresponds directly to the amplitude distribution. The other is formed for the sum of the initial field and the field shifted along a certain direction. The intensity distributions obtained allow one to calculate the two-dimensional structure of the field under study. It is noteworthy that the method requires no iteration procedures in solving the problem. This leads to speeding up of the processing and analysis of the information. Two variants of optical schemes for the analysis of light fields are considered. The first one corresponds to registration of the image of the analyzed plane and the second to registration of the spectrum of the spatial frequencies.     

Recycling solid supports – A head-to-tail linker

The concept of a `head-to-tail linker' designed to allow the regeneration and reuse of a variety of solid supports is introduced. The synthesis of this linker, its coupling to various solid supports, its application in a number of standard solid phase reactions and resin regeneration are presented.     

Phase Separation Driven by a Fluctuating Two-Dimensional Self-Affine Potential Field

We study phase separation in a system of hard-core particles driven by a fluctuating two-dimensional self-affine potential landscape which evolves through Kardar–Parisi–Zhang (KPZ) dynamics. We find that particles tend to cluster together on a length scale which grows in time. The final phase-separated steady state is characterized by an unusual cusp singularity in the scaled correlation function and a broad distribution for the order parameter. Unlike the one-dimensional case studied earlier, the cluster-size distribution is asymmetric between particles and holes, reflecting the broken reflection symmetry of the KPZ dynamics, and has a contribution from an infinite cluster in addition to a power law part. A study of the surface in terms of coarse-grained depth variables helps understand many of these features.     

Sulfur adsorption on Fe(1 1 0): a DFT study

The adsorption of atomic S on the Fe(1 1 0) surface is examined using density functional theory (DFT). Three different adsorption sites are considered, including the atop, hollow and bridge sites and the S is adsorbed at a quarter monolayer coverage in a p(2 × 2) arrangement. The hollow site is found to be the most stable, followed by the bridge and atop sites. At all three sites, S adsorption results in relatively minor surface reconstruction, with the most significant being that for the hollow site, with lateral displacements of 0.09 Å. Comparisons between S-adsorbed and pure Fe surfaces revealed reductions in the magnetic moments of surface-layer Fe atoms in the vicinity of the S. At the hollow site, the presence of S causes an increase in the surface Fe d-orbital density of states between 4 and 5 eV. However, S adsorption has no significant effect on the structure and magnetic properties of the lower substrate layers.     

Nature of the Peierls- to Mott-insulator transition in 1D

In order to clarify the physics of the crossover from a Peierls band insulator to a correlated Mott-Hubbard insulator, we analyze ground-state and spectral properties of the one-dimensional half-filled Holstein-Hubbard model using quasi-exact numerical techniques. In the adiabatic limit the transition is connected to the band to Mott insulator transition of the ionic Hubbard model. Depending on the strengths of the electron-phonon coupling and the Hubbard interaction the transition is either first order or evolves continuously across a narrow intermediate phase with finite spin, charge, and optical excitation gaps. Received 7 July 2002 / Received in final form 21 October 2002 Published online 27 January 2003 RID="a" ID="a"e-mail: holger.fehske@physik.uni-greifswald.de     

A new strategy for solid phase synthesis of a secondary amide library using sulfonamide linker via radical traceless cleavage

A new strategy for solid phase synthesis of a secondary amide library using sulfonamide linker via radical traceless cleavage is reported. Polystyrylsulfonyl chloride (1) reacted with primary amines to afford polystyryl-supported N-alkyl sulfonamides (2), which were acylated with acid chlorides and followed by radical cleavage with TiCl₄/Zn to afford secondary amides. It was interestingly found that the products released from acyl alkanesulfonamide resins are closely dependent on the substituents of benzene rings of alkyl or acyl groups on the resins. When the substituent on benzene ring of N-benzyl group of sulfonamides is an electron rich MeO-group, the products released from sulfonamide resins are dependent on the substitution position on benzene ring: para-MeO- to yield 1,2-bis (p-methoxylphenyl)ethane and N-p-methoxylbenzyl benzamide (30:1); ortho-MeO- to give 1,2-bis (o-methoxylphenyl)ethane and N-o-methoxylbenzyl benzamide (1:15); and meta-MeO- only to release N-m-methoxylbenzyl benzamide. Neither N-benzoyl sulfonamide resins on benzene ring with electron-drawing para-O₂N-, nor the one with electron-donating para-H₂N- could release any amide product, while the N-benzoyl sulfonamide resins on benzene ring with para-acetamido group released para-acetamidobenzamides. The conjugation effect to stabilize the radical groups in the radical cleaving process was observed.     

Shift-tolerance Property of Optical Security System using Phase-based Virtual Image

The shift-tolerance property of the encrypted image or the Fourier decrypting key in the Fourier space is proposed based on a phase-encoded virtual image. The encrypted data is obtained by the Fourier transform of the product of a phase-encoded virtual image to camouflage the original one and a random phase image. Therefore, even if unauthorized users analyze the encrypted image, they cannot reconstruct the required image. This virtual image protects the original one from being counterfeited and from unauthorized access. We demonstrate the robustness to data loss and shift of the encrypted data or the Fourier decrypting key in the proposed decryption technique using an interferometer.     

Effect of Detachments in Asymmetric Simple Exclusion Processes

Asymmetric simple exclusion processes are important for understanding low-dimensional multi-particle dynamic phenomena. The effect of irreversible detachments of particles on dynamics of asymmetric simple exclusion processes is studied using analytical and computer simulation techniques. In the simplest model, where particles can only detach from a single site in the bulk of the system, a theory is presented and used to calculate explicitly phase diagrams and particle density profiles. The complexity of the phase behavior is discussed in terms of a recent domain-wall theory for driven lattice systems. The theoretical results qualitatively and quantitatively agree with computer Monte Carlo simulations.     

二维直通道内气固两相流动的实验研究

本文利用频闪激光片光源摄像和图象处理技术，对二维直通道内气固两相流动进行了实验研究，定量测定了固体粒子的运动参数、运动速度、方向．测得了粒子的运动轨迹．并得出一些有价值的结论：在本实验范围内粒子基本上沿直线运动，并处于不断加速的状态；粒子与壁面碰撞的时间极短，反弹角小于碰撞角，反弹速率小于碰撞速率．从而获得了在不同的进口气流速度及不同的通道倾角下固体粒子与固体壁面碰撞的某些规律．得到了粒子与壁面相互作用的关系表达式．为理论计算打下了基础．