Structural properties and electron transfer reactivity of NX3/NX3+ (X=H, F) coupling systems
文献类型：期刊论文
| 作者 | Sun, Q; Qin, M; Bu, YX; Han, KL |
| 刊名 | journal of molecular structure-theochem
 |
| 出版日期 | 2005-02-14 |
| 卷号 | 714期号:2-3页码:165-174 |
| 关键词 | DFT calculations electron transfer reactivity activation energy coupling matrix element MP2 calculations contact distance dependence analysis |
| 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. |
| 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 |
| 收录类别 | SCI |
| 语种 | 英语 |
| WOS记录号 | WOS:000227105900013 |
| 公开日期 | 2015-11-10 |
| 源URL | [http://159.226.238.44/handle/321008/139770]  |
| 专题 | 大连化学物理研究所_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 |
| 推荐引用方式 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. |
入库方式： OAI收割
来源：大连化学物理研究所
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