The difference in the degree of localization between the LFMO and NBO basis sets, and its effects on the energy partitions
文献类型：期刊论文
| 作者 | Liu, XW; Bao, P; Ma, YP; Yu, ZH |
| 刊名 | JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM
 |
| 出版日期 | 2005-09-30 |
| 卷号 | 729期号:3页码:185-191 |
| 关键词 | Vertical Resonance Energy Localized Fragment Molecular Orbital Natural Bond Orbital Nbo Energetic Analysis Morokuma's Scf Energy Partition |
| ISSN号 | 0166-1280 |
| DOI | 10.1016/j.theochem.2005.04.010 |
| 英文摘要 | The LFMO (localized fragment molecular orbital) and NBO (natural bond orbital) basis sets are constructed. In the LFMO basis set, the sigma and pi systems are completely separated out, and each LFMO is absolutely localized on its own fragment. But, an NBO is only concentrated on its own fragment when it is expressed as the linear combination of AOs. Afterwards, the Morokum's SCF energy partition and the NBO energetic analysis are performed, over each of the LFMO and NBO basis sets, for the molecules in order to calculate their vertical resonance energy (Delta E-V). As shown by the theoretical data presented in this work, Delta E-V for molecule C6B6H6 is always destabilizing when it is obtained from the NBO energetic analysis over each of the LFMO and NBO basis sets, and the pi interaction between fragments has no effect on the energy of the sigma system (Delta E-sigma = 0). But, the values of Delta E-V, over the LFMO and NBO basis sets, are rather different. In the case, of the Morokuma's SCF energy partition, however, Delta E not equal 0 due to the electron coupling between the pi and sigma systems. As a result, Delta E-V for Molecule C6B6H6 become stabilizing, and Delta E-V obtained from the Morokuma's energy partition over the NBO basis set is greater in the absolute value than that over the LFMO basis set, indicating that the difference, in the degree of the localization, between the LFMO and NBO basis sets has a great effect on the electron coupling. In molecule C12H6, the vertical resonance energy Delta E-V, obtained from the NBO energetic analysis over each of the LFMO and NBO basis set, is always stabilizing. On the contrary, Delta E-V, obtained from the Morokum's energy partition over the NBO basis set, is stabilizing, but that, over the LFMO basis set, is destabilizing. According to the 4N + 2 rule, the NBO basis set is unreasonable for the, energy partition, and the NBO energetic analysis is unable to provide molecule with an reliable Delta E-V because it neglects the strong coupling between the pi and sigma systems. (c) 2005 Elsevier B.V. All rights reserved. |
| 语种 | 英语 |
| WOS记录号 | WOS:000232261900006 |
| 出版者 | ELSEVIER SCIENCE BV |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/57731]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Yu, ZH |
| 作者单位 | Chinese Acad Sci, Inst Chem, State Key Lab Struct Chem Unstable & Stable Speci, Beijing 100080, Peoples R China |
| 推荐引用方式 GB/T 7714 | Liu, XW,Bao, P,Ma, YP,et al. The difference in the degree of localization between the LFMO and NBO basis sets, and its effects on the energy partitions[J]. JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM,2005,729(3):185-191. |
| APA | Liu, XW,Bao, P,Ma, YP,&Yu, ZH.(2005).The difference in the degree of localization between the LFMO and NBO basis sets, and its effects on the energy partitions.JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM,729(3),185-191. |
| MLA | Liu, XW,et al."The difference in the degree of localization between the LFMO and NBO basis sets, and its effects on the energy partitions".JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM 729.3(2005):185-191. |
入库方式： OAI收割
来源：化学研究所
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