Direct Measurement of Charge Transfer Probability during Photodissociation of Few-keV OD + Beam.

We have measured the photodissociation of few-keV OD + molecular ions into either D + + O or O + + D final products. The three-dimensional momentum imaging measurements of the light and massive fragments in coincidence were enabled by using an upgraded two-detector setup. In this work, we show that absorption of a single 790 or 395 nm photon excites the OD + from its electronic ground state to the B Σ - 3 state, which dissociates to the O + ( 4 S) + D dissociation limit. To reach the other nearly degenerate dissociation limit, D + + O( 3 P), a unimolecular charge transfer, B Σ - 3 to X Σ - 3 , transition is required following the same photoexcitation. The measured branching ratio of these dissociation channels is a direct measure of the charge transfer transition probability. This measured probability as a function of energy above the dissociation limit agrees well with our calculations.