In this work we use non-adiabatic ab-initio molecular dynamics (NA-AIMD) simulations to investigate the hot exciton behavior within the first 200 fs after photo-excitation on sin-gle chains of an extended series of CPDT-donor-based polymers experimentally investigated by Tautz et al. (Figure ) in order to understand the effects of different donor-acceptor structures on the electron-hole interaction. By analyzing the photo-excitation dynamics in terms of (time-resolved) Coulomb attractive energy between the electron and hole density on one polymer chain and the (time-resolved) dipole moment, we investigate the ultrafast charge separation. We obtain detailed microscopic insights that systematically substantiate the analysis of experimental observations and correlate the charge-generation efficiency with the structures of the investigated donor-acceptor polymers. While the Coulomb attractive energy is used as a quantifier that can drive fast recombination, a polarized excited state with large dipole moment correlates with enhanced charge separation. Increasing the latter and reducing the former is identified as a viable strategy in the search for new promising materials for OPV devices.