In conclusion, polaron-pair formation is believed to play an important role as a possible precursor for subsequent charge separation at donor-acceptor interfaces or within aggregates in organic photovoltaic devices. In the present work we performed detailed NA-AIMD calculations on a series of different polymer structures previously investiagted experimentally to investigate the driving forces for polaron-pair formation at high excitation energies. Our results and discussion provide further evidence that the dipole moment of the excited (excitonic) state can be interpreted as an indicator for efficient initial polaron-pair formation. In contract, the Coulomb attractive energy appears to drive recombination. Thus, the former promotes subsequent charge separation, while the latter inhibits efficient charge generation.