Molecular Spectroscopy at Ultracold Temperatures

Associative ionization (AI) in sodium (Na + Na + 2 hv → Na2+ + e−) has been a convenient reaction in which to study excited state collisions under "ultracold" conditions (≤1 mK) because the reaction product is easily identified and collected with high signal-to-noise. Previous studies [1] have revealed evidence of molecular intermediate-state resonances under high-intensity laser conditions. Theoretical analysis [2] has associated this structure with singly- and doubly-excited Na2 intermediate states. In this work, we present a new technique utilizing a switched magneto-optical trap (MOT) to make clean measurements of the spectrum of associative ionization in a regime where we can identify the peaks as being associated with states of the Na2 molecule. In addition, our technique reveals new structure in the spectrum of AI versus laser frequency, pointing out the previously unappreciated importance of atomic hyperfine structure in the reaction.