We report the first observation of photoassociation to the 2(1)Sigma(g)(+) state of 85Rb2 . We have observed two vibrational levels (v=98, 99) below the 5s1/2+5p1/2 atomic limit and eleven vibrational levels (v=102-112) above it. The photoassociation---and subsequent spontaneous emission---occur predominantly between 15 and 20 Bohr in a region of internuclear distance best described as a transition between Hunds case (a) and Hunds case (c) coupling. The presence of a g-wave shape resonance in the collision of two ground-state atoms affects the photoassociation rate and lineshape of the J= 3 and 5 rotational levels.
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