共查询到17条相似文献,搜索用时 46 毫秒
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利用密度泛函理论方法研究了IClO2异构化反应机理. 优化得到了七种异构体, 其中OIClO和IClOO还未见报道, 对各异构体的热力学稳定性进行了比较. 找到了异构化过程的过渡态, 并通过内禀反应坐标(IRC)计算确认了各个异构体之间的相互转化关系. 从量子拓扑学的角度, 对典型异构化反应通道IRC途径上的各点进行了电子密度拓扑分析, 讨论了反应过程中化学键的断裂、生成以及化学键的变化规律, 找到了反应途径上的能量过渡态(ETS)和结构过渡态(STS). 相似文献
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ClO与ClO自由基反应机理及电子密度拓扑分析 总被引:1,自引:0,他引:1
利用密度泛函理论对ClO与ClO自由基反应机理进行了深入理论探讨,在B3LYP/6-311++G(3df)水平上对该反应体系的反应物、中间体、过渡态及产物进行了几何构型优化,对反应通道进行了IRC(内禀反应坐标)路径解析,计算了沿各反应通道的能垒和离解能,并进行了零点能校正.从量子拓扑学的角度,对反应通道IRC途径上一些重要点进行了电子密度拓扑分析,讨论了反应过程中化学键的断裂、生成以及键的变化规律,找到了反应途径的能量过渡态和结构过渡态. 相似文献
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采用MP4/6-311++G(d,p)和B3LYP/6-311++G(d,p)对磷叶立德CH2PH3和类磷叶立德自由基∙CHPH3进行构型优化,从电子密度拓扑分析的角度对C—P键的键结构进行了探讨。得到如下结论:类磷叶立德自由基和磷叶立德的C—P键性质类似,但磷叶立德中π键由两个电子形成,类磷叶立德自由基中π键由一个电子形成,所以前者的π性明显,而后者的π性不明显。类磷叶立德自由基中的这个单电子在碳原子附近,垂直于对称面的方向上运动,有p(C→P)配键的特征,所以类磷叶立德自由基∙CHPH3中的C—P键比相应的产物∙CH2PH2中的C—P键要弱一些。 相似文献
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BrO与CH3SH反应机理的量子化学及拓扑研究 总被引:1,自引:0,他引:1
利用密度泛函和电子密度拓扑分析方法对BrO与CH3SH反应的微观机理进行了理论研究. 在B3LYP/6-311G (d, p)水平上对反应势能面上的各驻点进行几何构型的全优化; 振动分析和IRC计算证实了中间体和过渡态的真实性和相互连接关系; 计算得到了各反应通道的活化能, 并进行了零点能校正. 计算结果表明: 该反应存在7个反应通道, 其中生成CH3S+HOBr和CH3SO+HBr的通道为主要反应通道. 通过对反应过程中部分驻点的电子密度拓扑分析, 首次发现了接近平面的四元环状过渡态, 从而拓展了原来对环状结构过渡态定义的适用范围. 相似文献
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利用密度泛函和电子密度拓扑分析方法对BrO与CH3SH反应的微观机理进行了理论研究. 在B3LYP/6-311G (d, p)水平上对反应势能面上的各驻点进行几何构型的全优化; 振动分析和IRC计算证实了中间体和过渡态的真实性和相互连接关系; 计算得到了各反应通道的活化能, 并进行了零点能校正. 计算结果表明: 该反应存在7个反应通道, 其中生成CH3S+HOBr和CH3SO+HBr的通道为主要反应通道. 通过对反应过程中部分驻点的电子密度拓扑分析, 首次发现了接近平面的四元环状过渡态, 从而拓展了原来对环状结构过渡态定义的适用范围. 相似文献
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Radical reactions : The ground‐state potential energy surface of the C2H5O system is investigated by ab initio methods using optimized geometries. The rate constants for the unimolecular isomerization and decomposition reactions of the three isomeric radicals (see picture) are calculated by microcanonical transition‐state theory at 200–3000 K, varying the pressures of the diluents.
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Mechanisms for the Breakdown of Halomethanes through Reactions with Ground‐State Cyano Radicals 下载免费PDF全文
Pooria Farahani Prof. Satoshi Maeda Prof. Joseph S. Francisco Dr. Marcus Lundberg 《Chemphyschem》2015,16(1):181-190
One route to break down halomethanes is through reactions with radical species. The capability of the artificial force‐induced reaction algorithm to efficiently explore a large number of radical reaction pathways has been illustrated for reactions between haloalkanes (CX3Y; X=H, F; Y=Cl, Br) and ground‐state (2Σ+) cyano radicals (CN). For CH3Cl+CN, 71 stationary points in eight different pathways have been located and, in agreement with experiment, the highest rate constant (108 s?1 M ?1 at 298 K) is obtained for hydrogen abstraction. For CH3Br, the rate constants for hydrogen and halogen abstraction are similar (109 s?1 M ?1), whereas replacing hydrogen with fluorine eliminates the hydrogen‐abstraction route and decreases the rate constants for halogen abstraction by 2–3 orders of magnitude. The detailed mapping of stationary points allows accurate calculations of product distributions, and the encouraging rate constants should motivate future studies with other radicals. 相似文献
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C_2h_3自由基与O_2反应机理的量子化学研究 总被引:1,自引:0,他引:1
用量子化学从头计算中UMP2(full)方法优化了C_2H_3自由基与O_2反应通道上 驻点(反应物、中间体、过渡态和产物)的几何构型,在Gaussian-3(G3)水平上计 算了它们的能量。在此基础上计算了该反应通道上各基元反应的反应活化能。通过 我们的研究发现,C_2H_3自由基与氧气反应存在着三元环、四元环和五元环反应机 理,且分别生成不同的产物,从反应活化能的计算结果扯CH_2O和CHO是反应的主要 产物,其次还可能生成CH_3 + CO_2, CH_2CO_2 + H, C_2H_2 + O_2H和COHCOH + H等产物,且它们生成几率逐渐减少,我们对生成产物CH_2O + CHO, CH_3 + CO_2, C_2H_2 + O_2H和COHCOH + H四条反应通道化学反应热的计算结果与实验吻 合较好。 相似文献
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The structures, stabilities and the isomerization reactions of CH3SO2 isomers in a doublet electronic state have been studied at B3LYP/6‐311+ +G (d,p), MP2/6‐311++G (d,p) and CCSD(T)/6‐311++G (d,p) levels. The three different levels of calculation give the similar results: thirteen minimum isomers were located and they were connected by eleven transition states. Among the thirteen isomers, cis‐CH3OSO, trans‐CH3OSO and CH3SO2 are the most stable species, and they should be detected easily in experiment. This is well consistent with the experimental result. These isomers could isomerize to each other by chemical bond vibration, chemical bond rotation and atom migration. The non‐planar ring structure transition state (STS), which was found in this paper, extended the concept of ring STS to the non‐planar systems. 相似文献
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采用B3LYP、MP2(full)和 QCISD 三种方法在6-311G(d, p)和aug-cc-pVDZ基组水平上对三线态O(3P)原子与CH2NH(s)的反应进行了详细的理论研究. 采用B3LYP和MP2(full)方法对反应势能面上的各驻点进行了几何构型优化, 通过振动频率分析证实了过渡态的真实性, 内禀反应坐标(IRC)跟踪验证了过渡态与反应物和产物的连接关系, 用上述三种方法计算得到了各反应通道的反应势垒. 对反应过程中的一些重要点进行了电子密度拓扑分析研究. 研究结果表明, O(3P)原子进攻CH2NH(s)中的N2原子和C1原子生成CH2NHO(t)和OCH2NH(t), CH2NHO(t)中N2上的H5可迁移到C1上异构化为CH3NO(t). 相似文献
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Lai‐Cai Li Jing Wang Xin Wang An‐Min Tian Ning‐Bew Wong 《International journal of quantum chemistry》2002,87(5):288-292
Ab initio calculations of the potential energy surface for the F + O3 and Cl + O3 reactions have been performed using the G3 and G3MP2 methods, which optimize the geometry configuration of reactants, products, intermediates, and transition states. The results show that fluorine atoms react with ozone as violently as chlorine atoms. At the same time, we have studied the reaction mechanisms of F atoms and Cl atoms with methane. It is found that fluorine atoms prefer to react with methane and chlorine atoms with ozone when there is competition between ozone and methane. Therefore, we can reasonably explain why chlorine atoms play the main role of reactants depleting ozone, while the more active fluorine atoms deplete less ozone. © 2002 Wiley Periodicals, Inc.; DOI 10.1002/qua.10119 相似文献