Extensive Theoretical Study on Electronically Excited States and Predissociation Mechanisms of Sulfur Monoxide Including Spin-Orbit Coupling
文献类型：期刊论文
| 作者 | Yu, Le1,2; Bian, Wensheng1 |
| 刊名 | JOURNAL OF COMPUTATIONAL CHEMISTRY
 |
| 出版日期 | 2011-06-01 |
| 卷号 | 32期号:8页码:1577-1588 |
| 关键词 | Electronically Excited States Spin-orbit Coupling Predissociation Curve Crossings Spectroscopic Constants |
| ISSN号 | 0192-8651 |
| DOI | 10.1002/jcc.21737 |
| 英文摘要 | The potential energy curves of the 69 Omega states generated from the 24 Lambda S states of sulfur monoxide are calculated for the first time using the internally contracted multireference configuration interaction method with the Davidson correction and the entirely uncontracted aug-cc-pV5Z basis set. Spin-orbit coupling is taken into account by the state interaction approach with the full Breit-Pauli Hamiltonian. Very good agreement is achieved between our computed spectroscopic properties and the available experimental data. The transition properties of the B-3 Sigma(-) -X-3 Sigma(-) and (4)1-X0(+) transitions are predicted, and our computed Franck-Condon factors and radiative lifetimes match the experimental results very well. The predissociation mechanisms are investigated, and various new predissociation channels are located. We present a new interpretation on the breaking-off of the rotational levels of the B-3 Sigma(-) lower vibrational states observed in experiment, and propose that the predissociation is induced by the Coriolis coupling between the B-3 Sigma(-) rovibrational levels and the A(3)Pi state. Our calculations indicate that, at nu' = 9, the B-3 Sigma(-) state predissociates via the C-3 Pi state; around nu' = 14, three spin-orbit-induced predissociation pathways via (1)(5)Sigma(+), (2)(5)Pi, and e(1)Pi would be open; around nu' = 17, the pathways via (2)(1)Sigma(+), (2)(3)Sigma(+) and (2)(5)Sigma(+) would contribute. These satisfactorily explain the experimental results about the diffuseness of the B-3 Sigma(-) bands. Furthermore, various predissociation pathways of the C'(3) P state are predicted, through which the C'(3)Pi state could predissociate rapidly. (C) 2011 Wiley Periodicals, Inc. J Comput Chem 32: 1577-1588, 2011 |
| 语种 | 英语 |
| WOS记录号 | WOS:000289429200009 |
| 出版者 | WILEY-BLACKWELL |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/71391]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Bian, Wensheng |
| 作者单位 | 1.Chinese Acad Sci, Inst Chem, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Beijing 100190, Peoples R China 2.Chinese Acad Sci, Grad Univ, Beijing 100049, Peoples R China |
| 推荐引用方式 GB/T 7714 | Yu, Le,Bian, Wensheng. Extensive Theoretical Study on Electronically Excited States and Predissociation Mechanisms of Sulfur Monoxide Including Spin-Orbit Coupling[J]. JOURNAL OF COMPUTATIONAL CHEMISTRY,2011,32(8):1577-1588. |
| APA | Yu, Le,&Bian, Wensheng.(2011).Extensive Theoretical Study on Electronically Excited States and Predissociation Mechanisms of Sulfur Monoxide Including Spin-Orbit Coupling.JOURNAL OF COMPUTATIONAL CHEMISTRY,32(8),1577-1588. |
| MLA | Yu, Le,et al."Extensive Theoretical Study on Electronically Excited States and Predissociation Mechanisms of Sulfur Monoxide Including Spin-Orbit Coupling".JOURNAL OF COMPUTATIONAL CHEMISTRY 32.8(2011):1577-1588. |
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来源：化学研究所
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