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Cope Rearrangement of 1,5-Hexadiene:  Full Geometry Optimizations Using Analytic MR-CISD and MR-AQCC Gradient Methods

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journal contribution
posted on 30.01.2003, 00:00 by Elizete Ventura, Silmar Andrade do Monte, Michal Dallos, Hans Lischka
Full geometry optimizations within given molecular symmetries have been performed on the chair and boat forms involved in the Cope rearrangement of 1,5-hexadiene using highly correlated methods (MR-CISD and MR-AQCC) and extended basis sets. These optimizations are based on analytic gradient procedures developed within the COLUMBUS program system and are the first ones for the Cope rearrangement, which have been carried out at a multireference, post-CASSCF level. By comparison of MR-CISD and MR-AQCC results, the importance of size-extensivity corrections is clearly demonstrated. Computed energetic stabilities with respect to 1,5-hexadiene and bis-allyl are in good agreement with experimental data. Only a single saddle point for the chair form of C2h symmetry is found in contrast to CASSCF results, but in agreement with CASPT2N and MRMP2 investigations. Thus, we confirm these previous results showing that the mechanism of the Cope rearrangement of 1,5-hexadiene is concerted via an aromatic transition state.