Ab initio研究3-羟基-2-亚膦基吡啶异构反应

在RHF/6 31G ,MP2 /6 31G ,RHF/6 311G和MP2 /6 311G水平上 ,对水分子作为催化剂参与下 3 羟基 2 亚膦基吡啶的异构化反应进行了研究 .计算所得Ea(RHF/6 31G) ,Ea(MP2 /6 31G) ,Ea(RHF/6 311G)和Ea(MP2 /6 311G)分别为 153.982 8,12 8.0 0 2 7,156 .96 19和 134.3916kJ·mol- 1,可见水分子作为催化剂参与下目标反应有较高的活化能 .     

Ab Initio研究3-硝基-2-吡啶酮异构反应

在RHF 6 31G和MP2 6 31G水平上 ,对 3 硝基 2 吡啶酮的气相、水分子作催化剂参与的异构化反应进行了研究 .计算所得气相异构和水分子作为催化剂参与反应过程的活化能分别为 2 0 5.80 2 0 (RHF 6 31G) ,157.2 2 0 5(MP2 6 31G)和 83.2 550 (RHF 6 31G ) ,57.1355(MP2 6 31G)kJ·mol-1.     

水二聚体分子间相互作用的理论研究

作者利用从头算方法,在HF/6 31G 水平下得到了水二聚体势能面上的7种优化构型,并经MP2法、均衡法(CP)分别校正了电子相关和基组叠加误差(BSSE),通过对分子中的原子间的最短距离、分子间质心距离与各构型相互作用能的关系进行了分析、比较,得到了最稳定的构型,其对应的分子间相互作用能为:-21.0205kJ·mol-1.     

1,3-丁二烯及呋喃与硫甲醛杂Diels-Alder反应的理论研究

采用量子化学从头算方法在 HF/6 - 31G*及 MP2 /6 - 31G*水平上对 1,3-丁二烯及呋喃与硫甲醛间的杂 Diels- Alder反应进行了理论研究 .利用能量梯度法对反应途径上各驻点的几何构型进行了优化 ,对过渡态进行了振动分析确认 .结果表明 :两反应均为双分子基元反应 ,两反应中牵涉到的前线轨道 (FMO)相互作用主要是 1,3-丁二烯或呋喃分子的最高占据轨道 (HOMO)与硫甲醛分子的最低空轨道 (L UMO)间的相互作用 ,在 MP2 /6 - 31G*水平所计算的两反应的活化势垒分别为 3.70 k J· mol- 1及 9.5 8k J· mol- 1 ,这与实验上所观察到的 1,3-丁二烯及呋喃容易与硫羰基化合物发生杂 Diels- Alder反应的实验现象是一致的 .     

酰基双烯酮重排反应的理论研究

采用量子化学从头算方法在 HF/6-3 1 G* *及 MP2 /6-3 1 G* *水平上计算了甲酰基双烯酮及苯甲酰基双烯酮的重排反应机理 .结果表明 ,两反应均为简单基元反应 ,反应中的 H原子 (或 C原子 )和邻近的 3个 C原子形成了具有四元环结构的对称过渡态 ,两反应的活化势垒分别为 1 5 0 .83 k J·mol- 1和 1 46.45 k J·mol- 1(MP2 /6-3 1 G* * 水平 ) ,这与苯甲酰基双烯酮需要在 5 5 0℃的高温下才能发生重排反应的实验事实一致 .     

1,3-丁二烯与硅甲基亚胺杂Diels-Alder反应的理论研究

采用量子化学从头算和密度泛函方法在HF/6-31G*及B3LYP6-31G*水平上对1,3-丁二烯与硅甲基亚胺间的杂Diels-Alder反应进行了理论研究.利用能量梯度法对反应途径上各驻点的几何构型进行了优化,对过渡态进行了振动分析确认.结果表明:该反应为一个由两步基元过程所构成的复杂反应,反应物首先经过一个无势垒过程形成中间复合物,此中间复合物然后经过过渡态闭环形成六元环产物,第二步过程的活化势垒为8.29kJ·mol-1(B3LYP/6-31G*).总反应为强放热过程.     

Combustion characteristics of unburned pulverized coal and its reaction kinetics with CO2

The combustion characteristics of two kinds of unburned pulverized coal (UPC) made from bituminous coal and anthracite were investigated by thermogravimetric analysis under air. The reaction kinetics mechanisms between UPC and CO₂ in an isothermal experiment in the temperature range 1000-1100℃ were investigated. The combustion performance of unburned pulverized coal made from bituminous coal (BUPC) was better than that of unburned pulverized coal made from anthracite (AUPC). The combustion characteristic indexes (S) of BUPC and AUPC are 0.47×10-6 and 0.34×10-6%2·min-2·℃-3, respectively, and the combustion reaction apparent activation energies are 91.94 and 102.63 kJ·mol-1, respectively. The reaction mechanism of BUPC with CO₂ is random nucleation and growth, and the apparent activation energy is 96.24 kJ·mol-1. By contrast, the reaction mechanism of AUPC with CO₂ follows the shrinkage spherical function model and the apparent activation energy is 133.55 kJ·mol-1.     

牛血清白蛋白与Cu~(2 ),Ca~(2 )相互作用的热化学研究

在310.15 K,pH=7.0的生理条件下,利用微量热法研究了牛血清白蛋白与Cu2 ,Ca2 相互作用,得到牛血清白蛋白与Cu2 的结合数为1;摩尔结合焓为-22.83 kJ·mol-1,摩尔结合自由能和熵分别为-66.024　kJ·mol-1和654.66　J·mol-1,而牛血清白蛋白与Ca2 则表现出较弱的相互作用.     

锰酸锂合成的动力学研究(Ⅰ)──氧气气氛

用热分析仪测试不同升温速率下,氢氧化锂和二氧化锰在氧气气氛中的差热分析曲线,结合DoyleOzawa法和Kissinger法研究锰酸锂合成的动力学;计算各反应阶段的表观活化能,依次为59462kJ·mol-1,92672kJ·mol-1,163271kJ·mol-1和107524kJ·mol-1·并确定反应级数,频率因子,速率常数,推导出每个反应阶段的动力学方程·为制备尖晶石型锰酸锂提供理论依据,进一步优化工艺条件·     

3-羟基-5-甲基-异噁唑异构化的量子化学研究

用密度泛函理论方法,在B3LYP/6-31G 水平上研究了3-羟基-5-甲基-异噁唑的异构化,优化了反应物、产物和过渡态的几何构型,采用MP2/6-31G 方法计算了单点能量,并用频率振动模式和内禀坐标(IRC)确证了过渡态的存在.     

Markedness and its Interpretation in Language Use

Language markedness is a common phenomenon in languages, and is reflected from hearing, vision and sense, i.e. the variation in the three aspects such as phonology, morphology and semantics. This paper focuses on the interpretation of markedness in language use following the three perspectives, i.e. pragmatic interpretation, psychological interpretation and cognitive interpretation, with an aim to define the function of markedness.     

低渗透非均质砂岩油藏启动压力梯度研究

理论推导与室内实验相结合,建立了低渗透非均质砂岩油藏启动压力梯度确定方法。首先借助油藏流场与电场相似的原理,推导了非均质砂岩油藏启动压力梯度计算公式。其次基于稳定流实验方法,建立了非均质砂岩油藏启动压力梯度测试方法。结果表明:低渗透非均质砂岩油藏的启动压力梯度确定遵循两个等效原则。平面非均质油藏的启动压力梯度等于各级渗透率段的启动压力梯度关于长度的加权平均;纵向非均质油藏的启动压力梯度等于各渗透率层的启动压力梯度关于渗透率与渗流面积乘积的加权平均。研究成果可用于有效指导低渗透非均质砂岩油藏的合理井距确定,促进该类油藏的高效开发。     

On Tragic Consciousness In The Works By Ernest Hemingway

As an American modern novelist who were famous in the literary world, Hemingway was not a person who always followed the trend but a sharp observer. At the same time, he was a tragedy maestro, he paid great attention on existence, fate and end-result. The dramatis personae's tragedy of his works was an extreme limit by all means tragedy on the meaning of fearless challenge that failed. The beauty of tragedy was not produced on the destruction of life, but now this kind of value was in the impact activity. They performed for the reader about the tragedy on challenging for the limit and the death.     

Achieving Unusual States of Matter Under High Pressure

正The periodicity of the elements and the non-reactivity of the inner-shell electrons are two related principles of chemistry,rooted in the atomic shell structure.Within compounds,Group I elements,for example,invariably assume the+1 oxidation state,and their chemical properties differ completely from those of the p-block elements.These general rules govern our understanding of chemical structures and reactions.Using first principles calcula-     

Exchange-Correlation and Electronic Excitation Energies from Pairing Matrix Fluctuations

We have developed an adiabatic connection to formulate the ground-state exchange-correlation energy in terms of pairing matrix linear fluctuations.This formulation of the exchange-correlation energy opens a new channel for density functional approximations based on the many-body perturbation theory.We illustrate the potential of such approaches with an approximation based on the particle-particle Random Phase Approximation(pp-RPA).This re-     

Density Functional Theory for the Response of Periodic Systems to Electric Fields Based on the Vector Potential Approach

正The electronic and nuclear(structural/vibrational)response of 1D-3D nanoscale systems to electric fields gives rise to a host of optical,mechanical,spectral,etc.properties that are of high theoretical and applied interest.Due to the computational difficulty of treating such large systems it is convenient to model them as infinite and periodic(at least,in first approximation).The fundamental theoretical/computational problem in doing so is that     

On the Thermodynamic Limit for Responses to Static Electromagnetic Fields

For molecular systems,the quantum-mechanical treatment of their responses to static electromagnetic fields usually employs a scalar-potential treatment of the electric field and a vector-potential treatment of the magnetic field.Although the potential for each field separately is associated with the choice of an(unphysical)origin,the precise choice of the origin for the electrostatic field has little consequences for the results.This is different for the     

An affordable accurate evaluation of the binding conformations predicted by molecular docking studies in bio-system

Franck-Condon factors bridge the gap between theoretical modeling and experimental observations for molecular electronic spectroscopy and electron transfer.Under the displaced harmonic oscillator approximation,multidimensional Franck-Condon factors are decomposed into a product of many one-dimensional(1D)Franck-Condon(FC)factors,and each 1D-FC factor is associated with one Huang-Rhys factor that determines the leading contribution of     

Call for Papers

<正>"The Journal of Shanghai Normal University:Mathematics"is published by Shanghai Normal University as regular issues of The Journal of Shanghai Normal University each year from 2014 in English.The editors-in-chief of the issues are professors Yuhao Cong and Maoan Han.The Journal of Shanghai Normal University was started in 1958 with     

Journal of Donghua University ( English Edition) Contents of Volume 31

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