TY - JOUR
T1 - The Diels-Alder reaction of ethene and 1,3-butadiene
T2 - An extended multireference ab initio investigation
AU - Lischka, Hans
AU - Ventura, Elizete
AU - Dallos, Michal
PY - 2004/9/20
Y1 - 2004/9/20
N2 - 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.
AB - 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.
KW - Ab initio calculations
KW - Biradical structures
KW - Correlation energies
KW - Multireference methods
KW - Reaction mechanisms
UR - http://www.scopus.com/inward/record.url?scp=5044252899&partnerID=8YFLogxK
U2 - 10.1002/cphc.200400104
DO - 10.1002/cphc.200400104
M3 - Article
C2 - 15499852
AN - SCOPUS:5044252899
SN - 1439-4235
VL - 5
SP - 1365
EP - 1371
JO - ChemPhysChem
JF - ChemPhysChem
IS - 9
ER -