We analyze a toy model for p-n junction photovoltaic devices by simulating photoexcited state dynamics in silicon nanowires. One nanowire is approximately circular in cross section with a diameter of d = 1.17 nm. The other has an approximately rhombic cross-section with d1 = 1.16 nm and d2 = 1.71 nm. Both nanowires have been doped with aluminum and phosphorus atoms and capped with gold leads. We use Boltzmann transport equation (BE) that includes phonon emission, carrier multiplication (CM), and exciton transfer. BE rates are computed using non-equilibrium finite-temperature many-body perturbation theory (MBPT) based on Density Functional Theory (DFT) simulations, including excitonic effects from Bethe-Salpeter Equation. We compute total charge transfer amount generated from the initial photoexcitation and find an enhancement when CM is included. In particular, we see between 78% and 79% enhancement in the smaller wire, while we see 116% enhancement in the larger nanowire