Taking also into account geometrical considerations, the dynamic dipole moment as the indicator of charge separation appears to be influenced by the geometrical arrangement of the polymers. While the dynamic dipole moment and thus the degree of polarization of PCPDT-BT I and PCPDT-2TBT are quite similar, the experimental observations indicate a somewhat lower polaron-pair yield for the latter. This suggests that although the dipole moment correlates with the polarized ICT character of the state, the spatial separation of the electron and hole wavefunction to form a polaron-pair state might be prevented by rotational barriers between the π-spacer and the donor and acceptor units, which planarize on the sub-ps timescale to produce ICT states. This shows that the complexity of the structure, especially rotational barriers between sub-units of the polymers, influences the separation of the electron and hole wavefunction and must be considered in addition to physical quantities such as the dipole moment.