Photoassociation of cold 87Rb(5s,fb = 2) atom pairs is studied within 13 GHz of the
dissociation limits 87Rb(5p3/2,fa)+87Rb(5s,fb = 2).
Vibrational levels in the long range, hyperfine manifolds of the 0g- and 1g states arising from
the 87Rb(5p3/2) fine structure limit are identified to lead to the formation of stable molecules
in the photoassociation process. The vibrational bands are observed to break off, at positions matching the energetic location
of potential-energy barriers predicted in the hyperfine manifolds at about 1 GHz above the
87Rb(5p3/2,fa = 3)+87Rb(5s,fb = 1) dissociation limit.
Empiricial potential-energy curves are derived from the data. These are found to be in agreement with predictions based on the
long-range hyperfine recoupling of the excited molecular states. The selectivity of the excitation process and predissociation mechanisms are discussed.
©2004 The American Physical Society