Journal ArticlePhotoassociation of ultracold lithium atoms into bound vibrational levels of the A 1Σu+ excited state is used to probe the X1Σg+ ground-state interaction potential of 6Li2 and 7Li2 . It had been predicted that the s-wave photoassociation signal strength would pass through a minimum as a function of vibrational level for positive s-wave scattering length. We report the observation of this novel effect, and use the location of the minimum to precisely determine the singlet s-wave scattering length for both isotopes. The sensitivity of this technique is demonstrated by distinguishing the minima for collisions involving 7Li atoms in different hyperfine states