Conformational and orientational analyses of 2,2′-bithiophene under interaction of external electric field constructed by point charges

The fully relaxed single-bond torsional potentials and orientation-related rotational potentials of 2,2′-bithiophene (BT) under the interaction of an external electric field (EF) constructed by point charges have been evaluated with semi-empirical AM1 and PM3 calculations. The torsional potentials are sensitive to both EF strength and direction. While the EF is parallel to the molecular long axis, the torsional barrier around Cα–Cα′ bond obviously rises with increasing the EF strength, whereas the relative energies of syn and anti minima show a slight change. The interaction between the EF and the induced dipole moment has been proposed to elucidate this observation. On the other hand, the relative energy difference between the syn and anti minima shows an obvious change, while the EF is perpendicular to the molecular long axis. This feature has been ascribed to the interaction between the EF and the permanent dipole moment of BT. Furthermore, conformational and orientational analyses in two dimensions have been carried out by changing the torsional and rotational angles in the different EF. The conformation and orientation of a gas-phase BT in the EF are governed by both the above factors.