Utility of Chemical Indices for Transition Structures of Pericyclic Reactions: Case Study of the Cope Rearrangement

Hiroshi Isobe, Shusuke Yamanaka, Kizashi Yamaguchi

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Stabilization effects of nonsynchronous transition structures (TSs) of the Cope rearrangements of phenyl-substituted 1,5-hexadienes were examined by the hybrid density functional theory (DFT) and UHF methods, Natural orbital analyses of the hybrid UDFT and UHF solutions were performed to analyze the instability of molecular orbitals at nonsynchronous TSs. It was found that the chemical characteristics at the TSs are made explicit in the behavior of the information entropy and related chemical indices, which are defined by the occupation numbers of natural orbitals. The computational results are discussed in connection with the utility of chemical indices and the applicability of the hybrid DFT methods for pericyclic reactions of large systems.

Original languageEnglish
Pages (from-to)532-545
Number of pages14
JournalInternational Journal of Quantum Chemistry
Volume95
Issue number4-5
DOIs
Publication statusPublished - Nov 15 2003
Externally publishedYes

Fingerprint

Density functional theory
hexadiene
density functional theory
orbitals
Molecular orbitals
occupation
molecular orbitals
Entropy
Stabilization
stabilization
entropy
1,5-hexadiene

Keywords

  • Chemical indices
  • Cooperative and competitive substituent effects
  • Cope rearrangement
  • Hybrid DFT

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Utility of Chemical Indices for Transition Structures of Pericyclic Reactions : Case Study of the Cope Rearrangement. / Isobe, Hiroshi; Yamanaka, Shusuke; Yamaguchi, Kizashi.

In: International Journal of Quantum Chemistry, Vol. 95, No. 4-5, 15.11.2003, p. 532-545.

Research output: Contribution to journalArticle

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