Coulomb blockade in molecular quantum dots

The rate-equation approach is used to describe sequential tunneling through a molecular junction in the Coulomb blockade regime. Such device is composed of molecular quantum dot (with discrete energy levels) coupled with two metallic electrodes via potential barriers. Based on this model, we calculate nonlinear transport characteristics (conductance-voltage and current-voltage dependences) and compare them with the results obtained within a self-consistent field approach. It is shown that the shape of transport characteristics is determined by the combined effect of the electronic structure of molecular quantum dots and by the Coulomb blockade. In particular, the following phenomena are discussed in detail: the suppression of the current at higher voltages, the charging-induced rectification effect, the charging-generated changes of conductance gap and the temperature-induced as well as broadening-generated smoothing of current steps.     

Chain length effect on dynamical structure of poly (vinyl pyrrolidone)-polar solvent mixtures in dilute solution of dioxane studied by microwave dielectric relaxation measurement

Dielectric relaxation study of the binary mixtures of poly(vinyl pyrrolidone) (PVP) (Mw=24000, 40000 and 360000 g mol⁻¹) with ethyl alcohol (EA) and poly(ethylene glycol)s (PEGs) (Mw=200 and 400 g mol⁻¹) in dilute solutions of dioxane were carried out at 10.1 GHz and 35°C. The relaxation time of PVP-EA mixtures was interpreted by the consideration of a wait-and-switch model in the local structure of self-associated ethyl alcohol molecules and also the PVP chain length as a geometric constraint for the reorientational motion of ethyl alcohol molecules. The formation of complexes and effect of PVP chain length on the molecular dynamics, chain flexibility and stretching of PEG molecules in PVP-PEG mixtures were explored from the comparative values of dielectric relaxation time. Further, relaxation time values in dioxane and benzene solvent confirm the viscosity independent molecular dynamics in PVP-EA mixtures but the values vary significantly with the non-polar solvent environment.     

Combinatorial computational chemistry approach of tight-binding quantum chemical molecular dynamics method to the design of the automotive catalysts

Recently, we have developed a new tight-binding quantum chemical molecular dynamics program “Colors” for combinatorial computational chemistry approach. This methodology is based on our original tight-binding approximation and realized over 5000 times acceleration compared to the conventional first-principles molecular dynamics method. In the present study, we applied our new program to the simulations on various realistic large-scale models of the automotive three-way catalysts, ultrafine Pt particle/CeO₂(111) support. Significant electron transfer from the Pt particle to the CeO₂(111) surface was observed and it was found to strongly depend on the size of the Pt particle. Furthermore, our simulation results suggest that the reduction of the Ce atom due to the electron transfer from the Pt particle to the CeO₂ surface is a main reason for the strong interaction of the Pt particle and CeO₂(111) support.     

Supramolecular chemistry

The article discusses molecular recognition and overviews the key concepts -storage and retrieval of chemical information by molecular structures, supramolecular reagents and catalysts, molecular transport, semiochemistry and self assembly. The prospects of controlling supramolecular architecture through engineered molecular recognition and design of ‘programmed systems’ controlled by molecular information are also discussed.     

吡啶团簇的多光子电离和离解研究

利用飞秒激光和飞行时间质谱结合从头计算对吡啶团簇的多光子电离和离解进行了研究. 给出了吡啶团簇的稳定结构和簇内的质子转移过程.     

Anharmonic effects in large-amplitude vibrations of metal clusters

Two types of extreme collective motion, large-amplitude many-phonon vibration of the ionic core and rotation of the cluster with high angular momenta, are considered. The interplay between vibration and collective motion towards fission is discussed. A new mechanism of formation and rupture of the neck is proposed which is based on the Franck-Condon principle, and accounts for the interplay between vibration and fission. Under rotation, the change of the shape of the cluster and a phase transition from axially symmetric to triaxial ellipsoid are predicted. For studying the effects, vibrational motion can be induced by laser radiation. Rotational motion may arise in collisions of clusters. Received 26 April 2001 and Received in final form 15 October 2001     

Towards understanding the increase in strength of thermotropic polyesters with heat treatment

Thermotropic copolyester fibers of oxynaphthoate and oxybenzoate have been subjected to conditions that promote solid-state polymerization as well as annealing. The annealing process causes the crystals to perfect with a simultaneous increase in heat of fusion and melting temperature. Solid-state polymerization, a reaction rate-controlled process, causes the polymer viscosity average molecular weight to increase by chain extension from about 14,000 g/mole to more than 87,000 g/mole with a simultaneous impressive increase in tenacity from about 10 g/d (1.2 GPa) to almost 30 g/d (3.7 GPa). To understand the changes in mechanical properties, we have modeled the fiber structure as short rod-like molecules poorly bonded to a continuous matrix of parallel molecules. Lengthening of the reinforcing molecules facilitates better transfer of load from matrix to molecules, resulting in higher tenacity fibers. © 1994 John Wiley & Sons, Inc.     

Influence of temperature on phosphorescence spectra of Pd-porphine in Shpol’skii matrices

We have studied the temperature dependence of the radiative deactivation of the Pd-porphine triplet states in Shpol’skii matrices in the temperature range 1.2–210 K. A substantial transformation of the phosphorescence spectra is observed as the temperature increases and is due to the inclusion of thermally activated Pd-porphine states in the radiative deactivation processes. The activation energy E_a of these Pd-porphine states is measured in matrices of n-octane and n-nonane. The splitting of the lowest quasidegenerate triplet state ΔE(T₂−T₁) is determined for planar and distorted conformations of the Pd-porphine macrocycle in the n-octane matrix as 40 and 57 cm⁻¹, respectively. The ability to use the temperature dependence of the phosphorescence properties of Pd-porphine to fabricate molecular thermometers for the low-temperature range is analyzed. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 4, pp. 460–464, July–August, 2007.     

核酸识体的研究及应用

核酸识体(aptamer)是近年来发展起来的一类经体外人工进化程序筛选出的寡聚核苷酸。它能高效、特异地结合各种配体，在蛋白质的分析检测、医学诊断治疗、生物传感器和分子开关的开发等方面有很大的应用前景，文章对核酸识体的研究和应用进展进行了综述。