Theoretical studies on the role of pi-electron delocalization in determining the conformation of N-benzylideneaniline with three types of LMO basis sets
文献类型：期刊论文
| 作者 | Bao, P; Yu, ZH |
| 刊名 | JOURNAL OF COMPUTATIONAL CHEMISTRY
 |
| 出版日期 | 2006-05-01 |
| 卷号 | 27期号:7页码:809-824 |
| 关键词 | Lfmo Basis Set Nbo Vertical Resonance Energy Morokuma's Energy Partition Conformation Of N-benzylideneaniline |
| ISSN号 | 0192-8651 |
| DOI | 10.1002/jcc.20390 |
| 英文摘要 | To understand the role of pi-electron delocalization in determining the conformation of the NBA (Ph-N=CH-Ph) molecule, the following three LMO (localized molecular orbital) basis sets are constructed: a LFMO (highly localized fragment molecular orbital), an NBO (natural bond orbital). and a special NBO (NBO-II) basis sets, and their localization degrees are evaluated with our suggesting index D-L. Afterward. the vertical resonance energy Delta E-v is obtained from the Morokuma's energy partition over each of three LMO basis sets. Delta E-v = Delta E-H (one electron energy) + Delta E-two (two electron energy), and Delta E-two = Delta E-Cou (Coulomb) + Delta E-ex (exchange) + Delta E-cc (or Sigma Delta E-n) (electron correction). Delta E-H is always stabilizing, and Delta E-Cou is destabilizing for all time. In the case of the LFMO basis set. Delta E-Cou is so great that Delta E-two > vertical bar Delta E-H vertical bar. Therefore, Delta E-v is always destabilizing, and is least destabilizing at about the theta = 90 degrees geometry. Of the three calculation methods such as HF, DFT, and MPn (it = 2, 3, and 4). the MPn method provides Delta E-v with the greatest value. In the case of the NBO basis set, on the contrary. Delta E-v is stabilizing due to Delta E-Cou being less destabilizing, and it is most stabilizing at a planar geometry. The LFMO basis set has the highest localization degree, and it is most appropriate for the energy partition. In the NBA molecule, pi-electron delocalization is destabilization. and it has a tendency to distort the NBA molecular away from its planar geometry as far as possible. (c) 2006 Wiley Periodicals, Inc. |
| 语种 | 英语 |
| WOS记录号 | WOS:000236944000001 |
| 出版者 | JOHN WILEY & SONS INC |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/58745]  |
| 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, State Key Lab Struct Chem Unstable & Stable Speci, Inst Chem, Beijing 100080, Peoples R China |
| 推荐引用方式 GB/T 7714 | Bao, P,Yu, ZH. Theoretical studies on the role of pi-electron delocalization in determining the conformation of N-benzylideneaniline with three types of LMO basis sets[J]. JOURNAL OF COMPUTATIONAL CHEMISTRY,2006,27(7):809-824. |
| APA | Bao, P,&Yu, ZH.(2006).Theoretical studies on the role of pi-electron delocalization in determining the conformation of N-benzylideneaniline with three types of LMO basis sets.JOURNAL OF COMPUTATIONAL CHEMISTRY,27(7),809-824. |
| MLA | Bao, P,et al."Theoretical studies on the role of pi-electron delocalization in determining the conformation of N-benzylideneaniline with three types of LMO basis sets".JOURNAL OF COMPUTATIONAL CHEMISTRY 27.7(2006):809-824. |
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来源：化学研究所
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