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题名: A theoretical study of the mechanism and kinetics of F+N-3 reactions
作者: Ma, Haitao;  Liu, Xiaojun;  Bian, Wensheng;  Meng, Lingpeng;  Zheng, Shijun
关键词: ab initio calculations ;  minimum energy crossing point ;  potential energy surfaces ;  rate constants ;  reaction mechanisms
刊名: CHEMPHYSCHEM
发表日期: 2006-08-11
DOI: 10.1002/cphc.200600183
卷: 7, 期:8, 页:1786-1794
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Physical ;  Physics, Atomic, Molecular & Chemical
研究领域[WOS]: Chemistry ;  Physics
英文摘要: Both the singlet((1)A') and triplet((3)A") potential energy surfaces (PESs) of F+N-3 reactions are investigated using the complete-active-space self-consistent field (CASSCF) and the multireference configuration interaction (MRCI) methods with a proper active space. The minimum energy crossing point (MECP) at the interaction seam between the 1A' and 2A" PESs is located and used to clarify the reaction mechanisms. Two triplet transition states are found, with one in the cis form and the other one in the trans form. Further kinetic calculations are performed with the canonical unified statistical (CUS) theory on the singlet PES and the improved canonical variational transition-state (ICVT) method on the triplet PES. The rate constants are also reported. At 298 K, the calculated rate constant is in reasonably good agreement with experimental values, and spin-orbit coupling effects lower it by 28%. The pectroscopic constants derived from the fitted potential-energy curves for the singlet states of NF are in very good agreement with values. Our calculations indicate that the adiabatic reaction on the singlet PES leading to NF(a1 Delta)+N2 is the major channel, whereas the nonadiabatic reaction through the MECP, which leads to NF(X-3 Sigma(-))+N-2, is a minor channel.
关键词[WOS]: POTENTIAL-ENERGY SURFACES ;  CONFIGURATION-INTERACTION CALCULATIONS ;  MULTIPHOTON IONIZATION SPECTROSCOPY ;  QUADRATIC STEEPEST DESCENT ;  AB-INITIO ;  RATE CONSTANTS ;  GROUND-STATE ;  MOLECULE REACTIONS ;  RYDBERG STATES ;  NF MOLECULE
语种: 英语
WOS记录号: WOS:000239884300027
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/140222
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Chinese Acad Sci, Inst Chem, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Beijing 100080, Peoples R China
2.Hebei Normal Univ, Dept Chem, Shijiazhuang 050016, Hebei, Peoples R China
3.Grad Univ Beijing, Chinese Acad Sci, Beijing 100049, Peoples R China

Recommended Citation:
Ma, Haitao,Liu, Xiaojun,Bian, Wensheng,et al. A theoretical study of the mechanism and kinetics of F+N-3 reactions[J]. CHEMPHYSCHEM,2006,7(8):1786-1794.
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