Reaction mechanism and kinetics of Criegee intermediate CH2OO with CH2 = C(CH3)CHO
文献类型：期刊论文
| 作者 | Cai, Jie1; Lu, Yousong1; Wang, Weina1; Chen, Long2; Liu, Fengyi1; Wang, Wenliang1 |
| 刊名 | COMPUTATIONAL AND THEORETICAL CHEMISTRY
 |
| 出版日期 | 2019-12-15 |
| 卷号 | 1170页码:8 |
| ISSN号 | 2210-271X |
| 关键词 | Criegee intermediate Methacrolein Reaction mechanism Rate constant Organic acids |
| DOI | 10.1016/j.comptc.2019.112644 |
| 通讯作者 | Wang, Wenliang(wlwang@snnu.edu.cn) |
| 英文摘要 | The comprehensive mechanism and kinetics for CH2OO with methacrolein (CH2 = C(CH3)CHO, MACR) reaction were investigated at the CCSD(T)/6-311 + G(2df,2p)//M06-2X/6-311 +G(2df,2p) level of theory. The results show that three kinds of mechanisms including cycloaddition, oxidation and insertion have been identified. Among them, the cycloaddition of CH2OO adding to C=O bond of MACR is more favorable, which occurs via a deeply submerged barrier leading to the formation of energized secondary ozonide (SOZ). The nascent SOZ mainly further decomposes into methacrylic acid and formaldehyde or formic acid and methacrolein, in which formic acid generation follows stepwise and concerted mechanism involving a catalysis for rearrangement of CH2OO by methacrolein. The calculated rate constant for the title reaction at 300 K using canonical variational transition state theory with small curvature tunneling correction is 1.00 x 10(-12) cm(3) molecule(-1) s(-1), which is close to the experimental value of (4.4 +/- 1.0) x 10(-13) cm(3) molecule(-1) s(-1). The results reveal that the reaction provides a new pathway to produce organic acids. However, the contribution of acids from this reaction is small as its relative lower rate, compared to atmospheric CH2OO loss occurring through the hydrolysis of CH2OO + (H2O)(n) (n = 1-2). |
| WOS关键词 | SECONDARY ORGANIC AEROSOL ; METHYL VINYL KETONE ; GAS-PHASE OZONOLYSIS ; DENSITY FUNCTIONALS ; POTENTIAL SOURCE ; CARBONYL OXIDES ; WATER DIMER ; ISOPRENE ; METHACROLEIN ; ACIDS |
| 资助项目 | National Natural Science Foundation of China[21473108] ; National Natural Science Foundation of China[21873060] ; National Natural Science Foundation of China[21636006] ; Fundamental Research Funds for the Central Universities[GK201901007] |
| WOS研究方向 | Chemistry |
| 语种 | 英语 |
| 出版者 | ELSEVIER |
| WOS记录号 | WOS:000501413400010 |
| 资助机构 | National Natural Science Foundation of China ; Fundamental Research Funds for the Central Universities |
| 源URL | [http://ir.ieecas.cn/handle/361006/13048]  |
| 专题 | 地球环境研究所_粉尘与环境研究室 |
| 通讯作者 | Wang, Wenliang |
| 作者单位 | 1.Shaanxi Normal Univ, Sch Chem & Chem Engn, Key Lab Macromol Sci Shaanxi Prov, Xian 710119, Shaanxi, Peoples R China 2.Chinese Acad Sci, Key Lab Aerosol Chem & Phys, SKLLQG, Inst Earth Environm, Xian 710061, Shaanxi, Peoples R China |
| 推荐引用方式 GB/T 7714 | Cai, Jie,Lu, Yousong,Wang, Weina,et al. Reaction mechanism and kinetics of Criegee intermediate CH2OO with CH2 = C(CH3)CHO[J]. COMPUTATIONAL AND THEORETICAL CHEMISTRY,2019,1170:8. |
| APA | Cai, Jie,Lu, Yousong,Wang, Weina,Chen, Long,Liu, Fengyi,&Wang, Wenliang.(2019).Reaction mechanism and kinetics of Criegee intermediate CH2OO with CH2 = C(CH3)CHO.COMPUTATIONAL AND THEORETICAL CHEMISTRY,1170,8. |
| MLA | Cai, Jie,et al."Reaction mechanism and kinetics of Criegee intermediate CH2OO with CH2 = C(CH3)CHO".COMPUTATIONAL AND THEORETICAL CHEMISTRY 1170(2019):8. |
入库方式： OAI收割
来源：地球环境研究所
浏览0
下载0
收藏0
其他版本
除非特别说明，本系统中所有内容都受版权保护，并保留所有权利。