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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
KeywordDft Calculations Electron Transfer Reactivity Activation Energy Coupling Matrix Element Mp2 Calculations Contact Distance Dependence Analysis
Source PublicationJOURNAL OF MOLECULAR STRUCTURE-THEOCHEM
2005-02-14
DOI10.1016/j.theochem.2004.09.043
Volume714Issue:2-3Pages:165-174
Indexed BySCI
SubtypeArticle
WOS HeadingsScience & Technology ; Physical Sciences
WOS SubjectChemistry, Physical
WOS Research AreaChemistry
WOS KeywordINNER-SPHERE REORGANIZATION ; DENSITY-FUNCTIONAL THEORY ; ION-MOLECULE REACTIONS ; AB-INITIO ; CORRELATION-ENERGY ; PROTON-TRANSFER ; RADICAL-CATION ; AMMONIA DIMER ; STATE ; GAS
AbstractThe 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.
Language英语
WOS IDWOS:000227105900013
Citation statistics
Document Type期刊论文
Identifierhttp://cas-ir.dicp.ac.cn/handle/321008/139770
Collection中国科学院大连化学物理研究所
Affiliation1.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
GB/T 7714
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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