Ab initio studies of isomerization and dissociation reactions of methyl peroxynitrate
文献类型：期刊论文
| 作者 | Wei, Wen-mei1; Zheng, Ren-hui2; Wu, Yun-kai1; Pan, Yue-li1; Yang, Fan1 |
| 刊名 | STRUCTURAL CHEMISTRY
 |
| 出版日期 | 2014-06-01 |
| 卷号 | 25期号:3页码:859-871 |
| 关键词 | Methyl Peroxynitrate Ab Initio Isomerization Dissociation Potential Energy Surface |
| ISSN号 | 1040-0400 |
| DOI | 10.1007/s11224-013-0351-9 |
| 英文摘要 | Using the CCSD(T)/cc-pVDZ//B3LYP/6-311G(2d,2p) method, we calculated the detailed potential energy surfaces (PESs) for the unimolecular isomerization and decomposition of methyl peroxynitrate (CH3O2NO2). The results show that there are the two most stable isomers, IS1a and IS1b, which are a pair of mirror image isomers. From IS1a and IS1b, different isomerization and unimolecular decomposition reaction channels have been studied and discussed. Among them, the predominant thermal decomposition pathways are those leading to CH3O2 + NO2 and cis-CH3ONO + O-2. The former is the lowest-energy path through the direct O-N bond rupture in IS1a or IS1b. The PES along the O-N bond in IS1a has been scanned, where the energy of IS1a reaches maximum value of 23.5 kcal/mol when the O-N bond is stretched to about 2.8 . This energy is 2.7 kcal/mol larger than the O-N bond dissociation energy (BDE) and 2.8 kcal/mol larger than the experimental active energy. In addition, because the energy barriers of IS1a isomerization to IS2a are 23.8 kcal/mol, close to the 20.8 kcal/mol O-N BDE in IS1a or IS1b, the isomerization reaction may compete with the direct bond rupture dissociation reaction. |
| 语种 | 英语 |
| WOS记录号 | WOS:000334514700018 |
| 出版者 | SPRINGER/PLENUM PUBLISHERS |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/53093]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Wei, Wen-mei |
| 作者单位 | 1.Anhui Med Univ, Coll Basic Med, Dept Chem, Hefei 230032, Anhui, Peoples R China 2.Chinese Acad Sci, Inst Chem, State Key Lab Struct Chem Unstable & Stable Speci, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China |
| 推荐引用方式 GB/T 7714 | Wei, Wen-mei,Zheng, Ren-hui,Wu, Yun-kai,et al. Ab initio studies of isomerization and dissociation reactions of methyl peroxynitrate[J]. STRUCTURAL CHEMISTRY,2014,25(3):859-871. |
| APA | Wei, Wen-mei,Zheng, Ren-hui,Wu, Yun-kai,Pan, Yue-li,&Yang, Fan.(2014).Ab initio studies of isomerization and dissociation reactions of methyl peroxynitrate.STRUCTURAL CHEMISTRY,25(3),859-871. |
| MLA | Wei, Wen-mei,et al."Ab initio studies of isomerization and dissociation reactions of methyl peroxynitrate".STRUCTURAL CHEMISTRY 25.3(2014):859-871. |
入库方式： OAI收割
来源：化学研究所
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