We report here measurements of two-body photoassociative ionization collisions between sodium atoms within an ultranarrow velocity class selected from a well-collimated, thermal atomic beam. Doppler-shifted excitation of the Na(3s
2S1/2;F=1)\ensuremath{\rightarrow}Na(5p
2P3/2) transition at 285 nm by a single-mode laser defines the narrow velocity class that subsequently populates the F=2 hyperfine level of the Na ground state by optical pumping. Probe laser beam excitation tuned near the Na(3s
2S1/2;F=2)\ensuremath{\rightarrow}Na(3p
2P3/2;F=3) transition produced photoassociative ionization with an average collision energy
EK corresponding to a temperature of 5.3 mK (
EK=3/2kT). We determine the rate constant for the process as a function of probe beam intensity and polarization.
Near threshold the microwave ionization rates of Na \ensuremath{\Vert}m\ensuremath{\Vert}=0,1 Rydberg states within a Stark manifold n show a strong dependence on the location of the state within the manifold. In particular, the rate-limiting step for ionization of states with the smallest Stark shifts (\ensuremath{\Vert}k\ensuremath{\Vert}\ensuremath{\ll}n) is different from the field-limited step of making the n\ensuremath{\rightarrow}n+1 transitions at threshold fields
FT\ensuremath{\simeq}1/3
n5 (a.u.). This variation in the ionization rates as a function of manifold location or Stark shift may be understood in terms of the variation in the transition probability to the bluest Stark states from the other members of the manifold.
The physics of the two-photon absorption process is investigated for a three-state system. The density-matrix equations for the two-photon interaction are solved in the steady-state limit assuming that the pump laser radiation is monochromatic. Collisional broadening, saturation, and Stark shifting of the two-photon resonance are investigated in detail by numerical solution of the steady-state density-matrix equations. Analytical expressions for the saturation intensity and the Stark shift are derived for the case where the single-photon transitions between the intermediate state and the initial and final states are far from resonance with the pump laser. For this case, it is found that the direction of the Stark shift is dependent on the relative magnitudes of the dipole-moment matrix elements for the single-photon transitions that couple the intermediate state with the initial and final states. Saturation and Stark shifting are also investigated for the case where the single-photon transitions between the intermediate state and the initial and final states are close to resonance with the pump laser.