We report the observation of direct, two-color photoassociative ionization (PAI) in collisions between
85Rb atoms optically cooled and confined in a magneto-optical trap. We also measure the resulting
R2+ ion spectrum and compare it to earlier trap-loss fluoresecence spectra. Unlike PAI in Na, which ionizes principally by collisional autoionization, the
Rb2∗ intermediate photoionizes directly to
Rb2+ in a fixed optical field. These observations confirm PAI as a sensitive and broadly applicable spectroscopic tool.
Ultrafast and narrow linewidth lasers are combined to study multiphoton photoassociative ionization (PAI) in a Rb magneto-optical trap. Through the use of time of flight spectroscopy and by varying the parameters of the ultrafast laser, the excitation pathway for PAI was determined. It was found that
Rb2+ is formed, not by direct photoionization, but by sequential excitation of
Rb2 to an autoionizing state. Determining the excitation and ionization pathway was a necessary first step for future efforts in trying to establish coherent control techniques, first for the efficient production of translationally cold
Rb2, and then for transferring population to a desired vibrationally cold molecular state.