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The pi-electron delocalization is destabilizing in N-(phenylethenylidene) benzeneamine; a method of separating out the pi and sigma systems in its ketenimine fragment
Yu, ZH; Xuan, ZQ
1999-10-01
Source PublicationJOURNAL OF MOLECULAR STRUCTURE-THEOCHEM
ISSN0166-1280
Volume488Pages:101-112
AbstractTo understand the nature of pi-electron delocalization, we have developed a new method of energy partition. As it is seen from our previous contributions devoted to stilbene-like species (J. Phys. Chem. A, 102 (1998) 2016-2028), whether the pi-electron delocalization is stabilization or not depends upon the response of the a framework to the delocalization, In the case of stilbene-like species, the quantum mechanical resonance energy is generally destabilizing. A method for separating out its pi and a systems in ketenimine fragment -CH=C=N- is a three-step procedure: (i) the dissection of the bridge -CH=C=N- into two fragments -CH=(P) and =C=N- (Q); (ii) two FMO basis sets psi'(pj) and psi'(qi) obtained from the full UHF computation for each of two fragments P and Q followed by the Kost's localization based on their respective fragment molecules H-CH=O and O=C=N-F; (iii) the superposition of psi'(pj) and psi'(qi) followed by two consecutive conditional UHF computations for fragment -CH=C=N- and a conditional RHF computation for fragment molecule H-CH=C=N-H at the STO-3G level. Based on our procedure, the Morokuma energy partitioning provides the various pi and a interaction energies. In each of the four hypothetical electronic states of the theta = 0 degrees geometry, the pi-electron delocalization is found to be destabilization. The DPI state is most destabilized. In the meantime, the delocalized pi system is always destabilized, and it is most destabilized in the FUD state. The pi-sigma orbital interaction is also destabilizing. The a-electron delocalization, on the other hand, strongly stabilizes the DSI state. The increase in the stability of the DSI states with the rotation of fragment C is discussed in detail, and it appears to confirm the concept: "stability" means "smaller destabilization" rather than "greater stabilization''. (C) 1999 Elsevier Science B.V. All rights reserved.
KeywordKetenimine Resonance Effect Separation Of The Pi And Sigma Systems Localization Of Fragment Molecular Orbitals Morokuma Energy Partition
Indexed BySCI
Language英语
WOS IDWOS:000082746400010
PublisherELSEVIER SCIENCE BV
Citation statistics
Cited Times:5[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://ir.iccas.ac.cn/handle/121111/74942
Collection中国科学院化学研究所
Corresponding AuthorYu, ZH
AffiliationChinese Acad Sci, Inst Chem, State Key Lab Struct Chem Unstable & Stable Speci, Beijing 100080, Peoples R China
Recommended Citation
GB/T 7714
Yu, ZH,Xuan, ZQ. The pi-electron delocalization is destabilizing in N-(phenylethenylidene) benzeneamine; a method of separating out the pi and sigma systems in its ketenimine fragment[J]. JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM,1999,488:101-112.
APA Yu, ZH,&Xuan, ZQ.(1999).The pi-electron delocalization is destabilizing in N-(phenylethenylidene) benzeneamine; a method of separating out the pi and sigma systems in its ketenimine fragment.JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM,488,101-112.
MLA Yu, ZH,et al."The pi-electron delocalization is destabilizing in N-(phenylethenylidene) benzeneamine; a method of separating out the pi and sigma systems in its ketenimine fragment".JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM 488(1999):101-112.
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