Abstract
The rotational barrier for substituted ethylenes was calculated with MO ab initio methods, both in the Hartree–Fock (HF) single determinant scheme and with multiconfigurational self-consistent field (MCSCF) approaches. The HF model affords reliable results only when applied to molecules substituted with strong electron donor groups, assigning a push–pull character to the molecule. The MCSCF approach was employed for calculating rotational barriers in poorly polarized ethylenes not directly amenable to the HF methods; however, this method was found hard to handle for low symmetry molecules with substituents interacting with the double bond. A method is proposed based on the interpolation of the energy of the perpendicular conformation from a Fourier truncated function constructed with HF molecular energies calculated for frozen conformations twisted up to 60°. The application of HF theory for studying internal rotation in substituted ethylenes with poorly polarized character is discussed and an upper limit of 35–40kcal/mol can be set up for having reliable barriers from the calculated energy of the rotational transition state at this level of theory.
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