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题名: Structural properties and electron transfer reactivity of NX3/NX3+ (X=H, F) coupling systems
作者: Sun, Q;  Qin, M;  Bu, YX;  Han, KL
关键词: DFT calculations ;  electron transfer reactivity ;  activation energy ;  coupling matrix element ;  MP2 calculations ;  contact distance dependence analysis
刊名: JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM
发表日期: 2005-02-14
DOI: 10.1016/j.theochem.2004.09.043
卷: 714, 期:2-3, 页:165-174
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Physical
研究领域[WOS]: Chemistry
英文摘要: The geometries and vibrational frequencies of NH3, NH3+, NF3, NF3+ as well as their encounter complexes (((NH3NH3)-N-...)(+) and ((NF3NF3)-N-...)(+)) are calculated using DFT and ab initio methods at 6-311 + +G** basis set level. This paper also discusses the inapplicability of DFT methods in predicting the dissociation energy curves, especially for the systems at large contact distance, due to the 'inverse symmetry breaking' problem. Finally, the contact distance dependence of the activation energy, the coupling matrix element and the electron-transfer rate has been analyzed at MP2/6-311 + + G** level. For the NX3/NX3+ (X = H, F) coupling systems, electron transfer occurs chiefly over a range of contact distance, 2.00 Angstrom < RN-N < 5.00 Angstrom. The optimum contact distances for the largest rates of electron transfer are 2.25 Angstrom for NH3/NH3+ system, and 2.22 Angstrom for NF3/NF3+ system. The corresponding maximum electron transfer rates are 1.94 x 10(6) s(-1) (NH3/NH3+) and 1.64 x 10(11) s(-1) (NF3/NF3+), respectively. In addition, it should be noted that the increase of the substituents attracting electrons to the active N centers favor electron transfer. (C) 2004 Elsevier B.V. All rights reserved.
关键词[WOS]: INNER-SPHERE REORGANIZATION ;  DENSITY-FUNCTIONAL THEORY ;  ION-MOLECULE REACTIONS ;  AB-INITIO ;  CORRELATION-ENERGY ;  PROTON-TRANSFER ;  RADICAL-CATION ;  AMMONIA DIMER ;  STATE ;  GAS
语种: 英语
WOS记录号: WOS:000227105900013
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/139770
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.Shandong Univ, Inst Theoret Chem, Jinan 250100, Peoples R China
2.Qufu Normal Univ, Dept Chem, Qufu 273165, Peoples R China
3.Acad China, Dalian Inst Chem Phys, Key State Lab Mol React Dynam, Dalian 116023, Peoples R China

Recommended Citation:
Sun, Q,Qin, M,Bu, YX,et al. Structural properties and electron transfer reactivity of NX3/NX3+ (X=H, F) coupling systems[J]. JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM,2005,714(2-3):165-174.
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