Crossed Molecular Beams and Quasiclassical Trajectory Surface Hopping Studies of the Multichannel Nonadiabatic O(P-3) + Ethylene Reaction at High Collision Energy
文献类型：期刊论文
| 作者 | Balucani, Nadia4; Leonori, Francesca4; Casavecchia, Piergiorgio4; Fu, Bina3; Bowman, Joel M.1,2 |
| 刊名 | JOURNAL OF PHYSICAL CHEMISTRY A
 |
| 出版日期 | 2015-12-17 |
| 卷号 | 119期号:50页码:12498-12511 |
| ISSN号 | 1089-5639 |
| DOI | 10.1021/acs.jpca.5b07979 |
| 文献子类 | Article |
| 英文摘要 | The combustion relevant O(P-3) + C2H4 reaction stands out as a prototypical multichannel nonadiabatic reaction involving both triplet and singlet potential energy surfaces (PESs)) which are strongly coupled. Crossed molecular beam (CMB) scattering experiments with universal soft electron ionization Mass spectrometric detection have been used to characterize the dynamics of this reaction at the relatively high collision energy E-c of 13.7 kcal/mol, attained by crossing the reactant beams at an angle of 135 degrees. This work is a full report of the data at the highest Ec investigated for this reaction. From laboratory product angular and velocity distribution measurements, angular and translational energy distributions in the center-of-mass system have been obtained for the five observed exothermic competing reaction channels leading to H + CH2CHO, H + CH3CO, CH3 + HCO, CH2 + H2CO, and H-2 + CH2CO. The product branching ratios (BRs) have been derived. The elucidation of the reaction dynamics is assisted by,synergic full-dimensional quasiclassical trajectory-Surface-hopping calculations of the reactive differential cross sections on coupled ab initio triplet/singlet PESs. This joint experimental/theoretical Study extends and complements Our previous combined CMB and theoretical work at the lower collision energy of 8.4 kcal/mol. The theoretically derived BRs and extent of intersystem crossing (ISC) are compared with experimental results. In particular, the predictions of the QCT results for the three main channels (those leading to virioxy + H, methyl + HCO and methylene + H2CO formation) are compared directly with the experimental data in the laboratory frame. Good overall, agreement is noted between theory and experiment, although some small, yet significant shortcomings of the theoretical differential cross section are noted. Both experiment and theory find almost an equal contribution from the triplet and singlet surfaces to the reaction, With a clear tendency of the degree of ISC to decrease with increasing E-c and with theory slightly overestimating the extent of ISC. |
| WOS关键词 | POTENTIAL-ENERGY SURFACES ; SOFT ELECTRON-IONIZATION ; REACTION DYNAMICS ; ATOMIC OXYGEN ; UNSATURATED-HYDROCARBONS ; BRANCHING RATIOS ; FORMALDEHYDE ; TRANSITIONS ; O(3P)+C2H4 ; SCATTERING |
| WOS研究方向 | Chemistry ; Physics |
| 语种 | 英语 |
| WOS记录号 | WOS:000366881000058 |
| 出版者 | AMER CHEMICAL SOC |
| 源URL | [http://cas-ir.dicp.ac.cn/handle/321008/171570]  |
| 专题 | 大连化学物理研究所_中国科学院大连化学物理研究所 |
| 通讯作者 | Casavecchia, Piergiorgio |
| 作者单位 | 1.Emory Univ, Dept Chem, Atlanta, GA 30322 USA 2.Emory Univ, Cherry L Emerson Ctr Sci Computat, Atlanta, GA 30322 USA 3.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China 4.Univ Perugia, Dipartimento Chim Biol & Biotecnol, I-06123 Perugia, Italy |
| 推荐引用方式 GB/T 7714 | Balucani, Nadia,Leonori, Francesca,Casavecchia, Piergiorgio,et al. Crossed Molecular Beams and Quasiclassical Trajectory Surface Hopping Studies of the Multichannel Nonadiabatic O(P-3) + Ethylene Reaction at High Collision Energy[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2015,119(50):12498-12511. |
| APA | Balucani, Nadia,Leonori, Francesca,Casavecchia, Piergiorgio,Fu, Bina,&Bowman, Joel M..(2015).Crossed Molecular Beams and Quasiclassical Trajectory Surface Hopping Studies of the Multichannel Nonadiabatic O(P-3) + Ethylene Reaction at High Collision Energy.JOURNAL OF PHYSICAL CHEMISTRY A,119(50),12498-12511. |
| MLA | Balucani, Nadia,et al."Crossed Molecular Beams and Quasiclassical Trajectory Surface Hopping Studies of the Multichannel Nonadiabatic O(P-3) + Ethylene Reaction at High Collision Energy".JOURNAL OF PHYSICAL CHEMISTRY A 119.50(2015):12498-12511. |
入库方式： OAI收割
来源：大连化学物理研究所
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