光解碎片平动谱中二级过程的运动学及化学动力学

本文发展了一套分析处理分子束光解反应实验中二级分解产物飞行谱的方法, 它改进了Kroger和Riley的最初讨论。本文表明许多重要的信息都可以从高度平均的实验数据中得出。这包括二级分解产物的平均平动能分布、空间各向异性参数、平行竞争通道间的反应比。模拟的结果可以表现二级分解反应的一些主要特征。     

Monte Carlo simulation of polarizable systems: Early rejection scheme for improving the performance of adiabatic nuclear and electronic sampling Monte Carlo simulations

An early rejection scheme for trial moves in adiabatic nuclear and electronic sampling Monte Carlo simulation (ANES-MC) of polarizable intermolecular potential models is presented. The proposed algorithm is based on Swendsen–Wang filter functions for prediction of success or failure of trial moves in Monte Carlo simulations. The goal was to reduce the amount of calculations involved in ANES-MC electronic moves, by foreseeing the success of an attempt before making those moves. The new method was employed in Gibbs ensemble Monte Carlo (GEMC) simulations of the polarizable simple point charge-fluctuating charge (SPC-FQ) model of water. The overall improvement in GEMC depends on the number of swap attempts (transfer molecules between phases) in one Monte Carlo cycle. The proposed method allows this number to increase, enhancing the chemical potential equalization. For a system with 300 SPC-FQ water molecules, for example, the fractions of early rejected transfers were about 0.9998 and 0.9994 at 373 and 423 K, respectively. This means that the transfer moves consume only a very small part of the overall computing effort, making GEMC almost equivalent to a simulation in the canonical ensemble.     

Structure formation and dynamics of water in strong external electric fields

We have performed molecular dynamics computer simulations of water in homogeneous external electric fields which were varied in a wide range of field strengths. The dielectric response is found to be linear up to fields E₀≈0.01 V/Å from where dielectric saturation effects become important. At fields of E₀≈3 V/Å a phase transition into an ordered, ice-like structure is observed, which is stabilized through hydrogen-bonds. With an increasing external electric field, the frequency spectrum of the water dynamics shows a remarkable red shift of the intramolecular modes and a blue shift of the librational motions, where the frequency varies quadratically with the field strength. A simple analytical model is discussed which reproduces the observed behavior.     

固液相变的分子动力学研究Ⅰ─—(KI)_(108)离子簇的熔化和凝固(英)

通过分子动力学模拟，考查并分析了（KI）108离子簇的结构、能量和相变的动力学行为．在加热和冷却过程中，离子簇再现了熔化和凝固现象，而且熔化起始于立方体的其一顶点，熔化的离子簇不是球形的，说明了离子簇的非湿特征．根据结晶的成核速率，讨论了电子衍射实验中观察KI凝固的可能性     

生物质裂解产物的制备及HPLC检测其成分的虚拟仿真实验开发

In order to improve university laboratory teaching and practical education under the background of information technology, as well as overcome the difficulty for practical training, develop a virtual simulation experiment platform for rapid pyrolysis of natal materials and high-performance liquid chromatographic (HPLC) detection of its components. The experiment integrates the actual operation process of the plant to produce cleaved products by rapid pyrolysis of biomass with HPLC detection. The virtual experiment is divided into biomass sample pretreatment, rapid biomass pyrolysis, bio-oil extraction, and HPLC determination of complex components, making the biomass cleavage workshop "real" through simulation. This virtual simulation experiment fully integrates the utilization of biomass resources and basic chemistry courses (such as organic chemistry, instrumental analysis, chemical engineering principles, etc.), which are widely involved in agricultural and forestry majors with advantageous characteristics value.     

Structure and hydration of polycytidylic acid from the data of infrared spectroscopy, EHF dielectrometry and computer modeling

The aim of this paper is to summarize the original results concerned with the elucidation of the role of water environment in the formation of different structures of polyribocytidylic acid (poly(rC)), depending on the pH, temperature and ion content. To solve this problem, we studied the hydration of poly(rC)-K⁺ in films differing in water content, by methods of infrared spectroscopy and piezogravimetry, and in solution, using the dielectric measurements at a wavelength of 7.6 mm (extremely high frequencies — EHF). The experimental results were confirmed by a Monte Carlo simulation of the interaction between water molecules and single-strand and double-strand poly(rC) fragments in clusters of 800 water molecules. A model of hydration of double-strand complex of poly(rC)⁺-poly(rC) has been proposed based on our results and the known X-ray parameters of the complex. The obtained results and proposed structure of poly(rC)⁺-poly(rC) suggest that, the stabilization of this complex occurs due to intra- and inter-chain water bridges, together with the hydrogen bonds between neutral and protonated cytosines in pairs.     

Monte‐Carlo simulation of spatial distribution of characteristic x‐rays in multi‐film targets: source size of Al Kα x‐rays in W/Al film targets

A Monte‐Carlo simulation approach has been applied to describe the spatial distribution of characteristic x‐rays in W/Al film targets of different combinations of film thicknesses for the optimal design of a small‐sized x‐ray source having a high x‐ray intensity. The result has led to optimal combinations of W and Al film targets for 100 kV electrons, e.g. W(1 µm)/Al(20 µm), W(3 µm)/Al(15 µm) and W(5 µm)/Al(8 µm). These Al/W targets could be used as x‐ray sources for a medical instrument currently under development. Copyright © 2004 John Wiley & Sons, Ltd.     

DFT study and Monte Carlo simulation on proton transfers of 2-amino-2-oxazoline, 2-amino-2-thiazoline, and 2-amino-2-imidazoline in the gas phase and in water

Density functional theory (DFT) and Monte Carlo (MC) simulation with free energy perturbation (FEP) techniques have been used to study the tautomeric proton transfer reaction of 2-amino-2-oxazoline, 2-amino-2-thiazoline, and 2-amino-2-imidazoline in the gas phase and in water. Two reaction pathways were considered: the direct and water-assisted transfers. The optimized structures and thermodynamic properties of stationary points for the title reaction system in the gas phase were calculated at the B3LYP/6-311+G(d, p) level of theory. The potential energy profiles along the minimum energy path in the gas phase and in water were obtained. The study of the solvent effect of water on the proton transfer of 2-amino-2-oxozoline, 2-amino-2-thiazoline, and 2-amino-2-imidazoline indicates that water as a solvent is favorable for the water-assisted process and slows down the rate of the direct transfer pathway.     

气相色谱过程的计算机模拟及操作条件的优化

建立了气相色谱过程的动态数学模型,给出了模型的实用算法,并据此对各种操作条件下的色谱流出曲线进行了动态模拟计算。模拟计算结果表明该模型是有效的,能够用于各种程序控制的色谱过程,可得到色谱分离的优化条件。