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Structural properties and electron transfer reactivity of NX3/NX3+ (X=H, F) coupling systems
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
2005-02-14
DOI10.1016/j.theochem.2004.09.043
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
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
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.
语种英语
WOS记录号WOS:000227105900013
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文献类型期刊论文
条目标识符http://cas-ir.dicp.ac.cn/handle/321008/139770
专题中国科学院大连化学物理研究所
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
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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.
APA Sun, Q,Qin, M,Bu, YX,&Han, KL.(2005).Structural properties and electron transfer reactivity of NX3/NX3+ (X=H, F) coupling systems.JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM,714(2-3),165-174.
MLA Sun, Q,et al."Structural properties and electron transfer reactivity of NX3/NX3+ (X=H, F) coupling systems".JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM 714.2-3(2005):165-174.
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