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Ab initio studies of 1,3-sigmatropic rearrangements: Effect of basis set and electron correlation

✍ Scribed by William R. Rodwell; Willem J. Bouma; Leo Radom

Publisher
John Wiley and Sons
Year
1980
Tongue
English
Weight
391 KB
Volume
18
Category
Article
ISSN
0020-7608

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✦ Synopsis

Abstract

Ab initio molecular‐orbital theory has been used to study the 1,3‐sigmatropic hydrogen rearrangements: propene → propene, formic acic → formic acid, and vinyl alcohol → acetaldehyde. Fully optimized structures of stable molecules and transition states have been determined using gradient procedures and the 4‐31G basis set. Improved energies have been obtained using a variety of techniques with basis sets up to the size of double‐ζ plus polarization (DZP) and electron correlation up to the CEPA/DZP level. Although both polarization functions and electron correlation lead to a lowering of the calculated barriers, the values remain substantial for all three rearrangements.

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