B. Jursic et Z. Zdravkovski, DFT STUDY OF THE DIELS-ALDER REACTIONS BETWEEN ETHYLENE WITH BUTA-1,3-DIENE AND CYCLOPENTADIENE, Perkin transactions. 2, (6), 1995, pp. 1223-1226
A set of DFT methods (Xa, HFB, S-VWN, B-LYP, B-HandH and Becke3-LYP) h
as been used for the calculation of the transition states and energy b
arriers of the Diels-Alder reaction of ethylene with buta-1,3-diene an
d cyclopentadiene. The pure DFT methods overestimate the bond lengths,
while the hybrid methods give values much-closer to those obtained by
conventional ab initio methods. The ratio of the sigma-forming bonds
to the pi-breaking bonds is in excellent correlation to the predicted
electronic energy barriers for these reactions. The local spin density
approximation (S-VWN) fails completely giving a negative value for th
e classical energy barrier height for the addition of ethylene to buta
-1,3-diene. On the other hand, the vibrational adiabatic barrier heigh
ts predicted by B-LYP/6-31G(*) and the hybrid Becke3-LYP/6-31G(**) th
eoretical models are in excellent agreement with available experimenta
l data for both reactions.