We use photoassociation of ultracold Na to study transitions from free atoms to bound molecules. We obtain rovibrational spectra of the 1(g), the 0(u)(+), and, for the first time, the 0(g)(-) "purely long-range" state of Na-2, all of which dissociate to Na(3 S-2(1/2))+Na(S P-2(3/2)).