The electron hole excitonic nature of high energy states is investigated in neutral and charged Si clusters, motivated by the multiple exciton generation (MEG) process that is highly debated in photovoltaic literature, Silicon forms the basis for-much of the photovoltaic industry, and our high-level, first principles calculations show that at 2-3 times the lowest excitation energy, the majority of optically excited states in neutral Si, and Si 10 take on multiple exciton (ME) character. The transition from single excitons (SEs) to MEs is not as sharp in Si as in PbSe clusters, but it is much more pronounced than in CdSe. The closer similarity of Si to PbSe than CdSe is unexpected, since Si clusters are less symmetric than PbSe clusters. Charging suppresses MEG in Si clusters; however, the suppression is less pronounced than in PbSe. A strong ME signal is seen already at 5 X E(g) upon charging. The low ME thresholds and nearly complete switch from SEs to MEs create a good possibility for efficient MEG in neutral Si nanoclusters and reveal hope that reasonable quantum yields can still be obtained despite charging.