Three band systems of Si2 have been found in absorption with a flash photolysis apparatus. Two of the band systems at 3200 and 2100 Å are new, whereas the third is an extension of the 3Σ–3Σ system observed by Douglas in emission. All three systems have the same lower state and arise from transitions. It is very probable that the state is the ground state of the Si0 molecule. Rotational and vibrational constants of all four 3Σ states have been determined. The dissociation energy of Si2 is estimated to be 3.0 ± 0.2 ev.