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Ab initio studies of 1,3‐sigmatropic rearrangements: Effect of basis set and electron correlation
Author(s) -
Rodwell William R.,
Bouma Willem J.,
Radom Leo
Publication year - 1980
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560180117
Subject(s) - ab initio , basis set , electronic correlation , chemistry , computational chemistry , formic acid , molecule , molecular orbital , sigmatropic reaction , polarization (electrochemistry) , ab initio quantum chemistry methods , density functional theory , stereochemistry , organic chemistry
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.