排序方式: 共有31条查询结果,搜索用时 46 毫秒
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采用密度泛函理论方法B3LYP/cc-pVTZ,对模型化合物2,3,4-羟基丁醛的脱羰基和2,3,4-羟基丁酸的脱羧基反应机理进行了量子化学理论研究。对两种模型化合物分别设计了三种热解反应途径,计算了不同温度下各热解反应途径的标准热力学及动力学参数。计算结果表明,纤维素热解过程中CO2和CO的逸出分别与脱羧基和脱羰基反应相对应,脱羧基和脱羰基反应均为分子内氢原子转移的协同过程。脱羰基反应是吸热反应,而脱羧基反应是放热反应。饱和丁醇醛的脱羰基反应反应能垒为288.8 kJ/mol,脱水后的不饱和烯醇醛的脱羰基反应能垒增大;饱和丁醇酸的脱羧基反应能垒较高,为303.4 kJ/mol,脱水后的不饱和烯醇酸的脱羧基反应能垒明显减小,这说明脱水有利于CO2的生成。 相似文献
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采用密度泛函理论方法 B3LYP/6-31G++(d,p),对纤维素的一个循环单体β-D-吡喃葡萄糖的热解反应机理进行了量子化学理论研究。设计了四种可能的热解反应途径,对各种反应的反应物、产物、中间体和过渡态的结构进行了能量梯度全优化,计算了各热解反应途径的标准动力学参数。计算结果表明,反应路径1中速控步的活化能为297.02 kJ.mol,反应路径2中速控步的活化能为284.49 kJ.mol,与反应路径3,4相比,反应路径1,2的反应能垒更低,是主要的热解反应通道,乙醇醛、1-羟基-2-丙酮、5-羟甲基糠醛、CO等小分子产物是热解的主要产物。这与相关实验结果分析是一致的。 相似文献
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基于微观IBM理论,提出转动诱导出玻色子量子相变的一种可能途径:一旦原子核在受到高能激发或作快速旋转时,假如外界提供的能量足以使玻色子完成拆对顺排,则核处于集体相与单粒子态的共存相,其特征是出现较密集的能谱;假如能量不足以完成拆对或顺排,可能发生两种情况之一,当核旋转达到某个临界转动频率ωc时,或者一个高角动量的玻色子脱离“集体”而“游离”出来,或者发生一个高角动量的玻色子转变为一个低角动量的玻色子,核仍旧处于集体相;均会伴随出现光辐射,产生基态带的一条能级——相变信号.正是这类玻色子相变导致了原子核的量子相变.本物理图像统一了玻色子拆对顺排相变和退耦释放光子相变的描述.以100Pd核的14+1,14+2和14+3态的产生机理为例,对模型作了仔细说明. 相似文献
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156Gd基态SU(3)→O(6)相变的一种微观理解 总被引:1,自引:0,他引:1
γ射线能量自旋曲线指认156Gd核基态具有SU(3)和O(6)两种对称性。 基于微观sdIBM-max方案和单粒子能量实验值, 用两组核子之间的对作用、 四极对作用、 四极 四极作用的等效强度参数, 都很好地再现了这两种能谱及其演化过程。 计算结果揭示出对基态相变的一种新理解: SU(3)的基准态是低激发 低有序态, 而O(6)基准态则是高激发 高有序的, 它们有临界区6+1—8+1态; 当核退耦到临界区时, 高有序基准态释放多余的有序结构能, 导致低有序基准态重组, 实现减速旋转驱动高有序核向着低有序核过渡的量子相变。最后用156Gd核的势能曲面作了直观说明。 The γ ray energy over spin curves identifies that there are the SU(3) and O(6) symmetries in the ground states of the 156Gd nucleus; by means of the microscopic sdIBM max approach and signal particle experimental energies the spectra of those two symmetries and their transient process are successfully reproduced through two parameters of nucleon nucleon effective interaction with pairing plus quadrupole pairing plus quadrupole quadrupole forces. The calculated results reveal a new way to recognize ground states quantum phase transition, in which the basic state of the SU(3) symmetry is a low lying and low ordered state, while one of the O(6) are a high lying and high ordered state, their critical region is between 6+1—8+1 states, the high ordered basic state releases spare ordered structure energy, reducing rotation speed, thus causing the restructure of low ordered basic state and accomplishing the quantum phase transition from the high ordered phase into the low ordered phase, the shape phase transition takes place along the yrast line of nucleus when it de excited to the critical region. Because the structural phase transition takes place by no obvious charge of boson structure constants in the critical region it is a benignancy and calm transition with respect to its macroscopic behave. The potential energy surface of 156Gd nucleus has been illustrated to visualize. 相似文献
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Spectral property and its shape transition on 72—84Kr isotopes in microscopic core plus two—quasiparticle approach 下载免费PDF全文
By using a microscopic sdIBM-2+2q.p. approach, the levels of the ground-band, γ-band and partial two-quasi-particle bands for {}^{72-84}Kr isotopes are calculated. The data obtained are in good agreement with the recent experimental results, and successfully reproduce the nuclear shape phase transition of {}^{72-84}Kr isotopes at zero temperature. The ground-state band is described successfully up to J^π=18^+ and E_x=10.0MeV. Based on this model, the aligned requisite minimum energy has been deduced. The theoretical calculations indicate that no distinct change of nuclear states is caused by the abruptly broken pair of a boson, and predict that the first backbending of Kr isotopes may be the result of aligning of two quasi-neutrons in orbit g_{9/2}, which gains the new experimental support of the measurements of g factors in the {}^{78-86}Kr isotopes. 相似文献
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采用密度泛函理论B3LYP/6-311G(d)方法,对聚苯乙烯(PS)热降解反应机理进行了研究。PS热降解的主要产物是苯乙烯,其次是甲苯、α-甲基苯乙烯、乙苯和二聚体等芳烃化合物。PS热降解反应主要包括主链C-C键均裂、β-断裂、氢转移和自由基终止等反应。针对以上各类反应进行了路径设计和理论计算分析,对参与反应的分子的几何结构进行了优化和频率计算,获得了各热降解路径的标准动力学和热力学参数。计算结果表明,苯乙烯主要由自由基的链端β-断裂反应形成;二聚体主要由分子内1,3氢转移的反应形成;α-甲基苯乙烯由分子内的1,2氢转移后进行β-断裂形成;甲苯由苯甲基自由基夺取主链上的氢原子形成;乙苯由苯乙基自由基夺取氢原子形成。动力学分析表明,苯乙烯形成所需要的能垒低于其他产物形成所需要的能垒,故苯乙烯为主要的热降解产物;这与相关实验结果基本一致。 相似文献
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