| 大气中Cl原子与甲基乙烯基酮反应机理的理论研究 |
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| 引用本文： | 韩廷峰,张为超. 大气中Cl原子与甲基乙烯基酮反应机理的理论研究[J]. 徐州师范大学学报(自然科学版), 2014, 0(1): 64-70 |
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| 作者姓名： | 韩廷峰 张为超 |
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| 作者单位： | 江苏师范大学化学化工学院,江苏徐州221116 |
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| 基金项目： | 江苏省高校自然科学基金资助项目（10KJB150017） |
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| 摘 要： | 采用CCSD(T)/6-31+G(d,p)//BHHLYP/6-311++G(d,p)+0.9335×ZPE理论方法,构建了在O2/NO存在的情况下Cl原子与甲基乙烯基酮反应的势能面剖面图.该反应体系的势能面上存在多个可能的反应途径,包括直接氢抽提通道和加成-消除通道.计算结果表明:在初始反应通道中,最可行的反应途径是生成加合物CH3C(O)CHCH2Cl(IM1)和CH3C(O)CHClCH2(IM2).在大气条件下,新形成的加合物IM1和IM2可以进一步与O2/NO发生反应,生成最终的主要产物氯乙醛(CH2ClC(O)H)和甲醛(HC(O)H),这与实验中检测到的主要产物是一致的.
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| 关 键 词： | 甲基乙烯基酮 Cl原子 反应机理 BH&HLYP 耦合簇理论 |
Theoretical study on the reaction mechanism of Cl atom with methyl vinyl ketone in the atmosphere |
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| Han Tingfeng,Zhang Weichao. Theoretical study on the reaction mechanism of Cl atom with methyl vinyl ketone in the atmosphere[J]. Journal of Xuzhou Normal University(Natural Science Edition), 2014, 0(1): 64-70 |
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| Authors: | Han Tingfeng Zhang Weichao |
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| Affiliation: | (School of Chemistry Chemical Engineering,Jiangsu Normal University,Xuzhou 221116,Jiangsu,China) |
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| Abstract: | The potential energy surfaces for the Cl＋methyl vinyl ketone reaction in the presence of O2/NO are theo-retically characterized at the CCSD（T）/6-31＋G（d,p）//BH＆amp;HLYP/6-311＋＋G（d,p）＋0. 9335 ＆#215;ZPE level of theory.Various possible pathways including the direct hydrogen abstraction channels and the addition-elimination channels are considered. The calculations show that the feasible channels are the formation of adducts CH3C（O）CHCH2Cl （IM1）and CH3C（O）CHClCH2（IM2）in the initial reaction pathways.In the atmosphere,the newly formed adducts IM1 and IM2 can further react with O2/NO to form the dominant products chloroacetaldehyde CH2 ClC（O）H and formaldehyde HC（O）H.The calculated results confirm the experimental studies. |
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| Keywords: | BH＆amp HLYP methyl vinyl ketone chlorine atom reaction mechanism BH＆amp HLYP |
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