Dipole moments of conjugated donor–acceptor substituted systems: calculations vs. experiments

We find that quantum mechanical calculations using B3LYP/aug-cc-pVTZ model chemistry involving anharmonic correction on simple conjugated organic compounds without rotating moieties provide the dipole moment values and molecular geometries with high accuracy. In the presence of one or two conjugated electron donating or accepting substituents capable of hindered rotation, the calculated dipole moments reproduce the experimental results equally well only in the cases when the experiments were done at the temperatures at which rotation of substituents remains hindered. In order to reproduce the experimental dipole moments determined at higher temperatures, a model assuming free (unhindered) rotation should be applied. In these cases, the contribution of each rotamer is equal and using anharmonic correction is not necessary. The APFD functional produces similar results and the M062X functional yields larger deviations from the experimental data. The other methods, like HF and MP2, are the least accurate with the basis sets usually employed for interpreting the experimental data.