A new laser spectroscopic technique has been demonstrated for examining the structure of alkali--rare gas diatomic electronic states near the classical limit. In two-color experiments, Rb--Ar or Rb--Kr thermal pairs are excited by free
leftarrowfree or bound
leftarrowfree transitions while monitoring the amplified spontaneous emission produced on the Rb D
1 or D
2 lines. Spectra observed lying within 10 cm
−1 of the separated atom limit for the A
2Pi1/2 states of Rb--Ar and Rb--Kr will be presented and discussed.