The Cope Rearrangement Revisited with Multireference Perturbation Theory

P. M. Kozlowski, M. Dupuis, E. R. Davidson

Research output: Contribution to journalArticle

103 Citations (Scopus)

Abstract

Earlier calculations on the Cope rearrangement based on a CASSCF wave function for the six electrons in the rearranging bonds gave reasonable energies at most places on the potential surface except in the crucial region around the chair transition state. Recently developed MP2 methods for multireference wave functions yield greatly improved energies. Using our version of this method, we simultaneously find that the CASSCF wave function overestimates the diradical character of the wave function. When this error is corrected, the Dewar-type diradicaloid stable intermediate no longer occurs as a minimum in the potential surface and the aromatic transition state moves to shorter bond lengths.

Original languageEnglish
Pages (from-to)774-778
Number of pages5
JournalJournal of the American Chemical Society
Volume117
Issue number2
DOIs
Publication statusPublished - Jan 1995

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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