CH_2X(X=H,FCI)与臭氧反应机理的最子化学研究 |
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引用本文: | 李来才,邹勤,田安民. CH_2X(X=H,FCI)与臭氧反应机理的最子化学研究[J]. 化学学报, 2003, 61(10): 1524-1527 |
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作者姓名: | 李来才 邹勤 田安民 |
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作者单位: | 李来才(四川师范大学化学系,成都,610066);邹勤(四川师范大学化学系,成都,610066);田安民(四川大学化学系,成都,610064) |
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基金项目: | 国家自然科学基金(No.29873029)和四川省教委重点资助项目. |
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摘 要: | 用量化学UMP2方法,在6-311++G**基组水平上研究了CH_2X(X=H,FCI)与臭氧反 应机理,全参数优化了反应过程中反应物、中间体、过渡态和产物的内何构型,在 UQCISD(T)/6-311++G**水平上计算了它们的能量,并对它们进行了振动分析,以 确定中间体和过渡态的直实性。从CH_2X(X=H,FCI)与O_3的反应机理的研究结果看 ,它们与O_3反应的活性都比较强,相对而言,活性大小顺序为CH_2F>CH_3> CH_2CI,也就是说,CH_2F自由基与臭氧间的反应活性最强,对大气臭氧的损耗将 是最大的。同时研究还发现CH_2X(X=H,FCI)系列自由基与O_3的反应都是强放热反 应。
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关 键 词: | 臭氧 反应机理 活化能 卤代烃 甲烷 P 游离基 |
修稿时间: | 2003-04-25 |
Study on the Quantum Chemistry of CH_2X(X=H,F,CI) and O_3 Reaction Mechanism |
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Affiliation: | Department of Chemistry, Sichuan NormalUniversity;Department of Chemistry, Sichuan University |
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Abstract: | Quantum chemistry UMP2 method was performed to stu dy the reaction mechanism of the reactions of CH 2X (X=H, F, Cl) with O 3. The g eometric configurations of reactants, intermediates, transition states and produ cts were optimized by UMP2 method at 6-311++G ** level and the energies o f stationary points along the pathways were calculated at UQCISD(t)/6-311++G ** level. Intermediates and transition states were confirmed by vibration an alysis. From the results of the reaction mechanism of the reactions of CH 2X (X =H, F, Cl) with O 3, one can see that they are active radicals depleting ozone and the order of activity is CH 2F>CH 3>CH 2Cl. That is to say, CH 2F is t he most active chemical of the three radicals depleting the ozone layer. It is a lso found that the reactions of CH 2X (X=H, F, Cl) with O 3 are strongly e xothermic. |
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Keywords: | OZONE REACTION MECHANISM ACTIVATION ENERGY HALOHYDROCARBON METHANE P FREE RADICAL |
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