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Utility of chemical indices for transition structures of pericyclic reactions: Case study of the cope rearrangement
Author(s) -
Isobe Hiroshi,
Yamanaka Shusuke,
Yamaguchi Kizashi
Publication year - 2003
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.10782
Subject(s) - pericyclic reaction , cope rearrangement , atomic orbital , chemistry , transition state , density functional theory , quantum chemical , computational chemistry , molecular orbital , statistical physics , molecule , thermodynamics , quantum mechanics , physics , stereochemistry , organic chemistry , catalysis , electron
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. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003