The Diels-Alder reaction of ethene and 1,3-butadiene: An extended multireference ab initio investigation

Hans Lischka, Elizete Ventura, Michal Dallos

Research output: Contribution to journalArticle

36 Scopus citations

Abstract

The concerted and stepwise mechanisms of the Diels-Alder reaction between 1,3-butadiene and ethene have been investigated using highly correlated multireference methods (MRAQCC) and extended basis sets. Full MRAQCC geometry optimizations have been performed in all cases. The best estimate for the energy barrier of the Diels-Alder reaction is 22 kcal mol-1. Anti- and gauche-out minima for the biradical structures and corresponding fragmentation saddle points have been determined. The biradical anti fragmentation saddle point is located 6.5 kcal mol-1 above the concerted saddle point. The gauche-in structure does not correspond to a local minimum, but leads on geometry optimization directly to cyclohexene.

Original languageEnglish
Pages (from-to)1365-1371
Number of pages7
JournalChemPhysChem
Volume5
Issue number9
DOIs
StatePublished - Sep 20 2004

Keywords

  • Ab initio calculations
  • Biradical structures
  • Correlation energies
  • Multireference methods
  • Reaction mechanisms

Fingerprint Dive into the research topics of 'The Diels-Alder reaction of ethene and 1,3-butadiene: An extended multireference ab initio investigation'. Together they form a unique fingerprint.

Cite this