Zero kinetic energy-pulsed field ionization and resonance enhanced multiphoton ionization photoelectron spectroscopy: Ionization dynamics of Rydberg states in HBr

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Abstract
The results of rotationally resolved resonance enhanced multiphoton ionizationphotoelectron spectroscopy and zero kinetic energy‐pulsed field ionization studies on HBr via various rotational levels of the F 1Δ2 and f 3Δ2Rydberg states are reported. These studies lead to an accurate determination of the lowest ionization threshold as 94 098.9±1 cm−1. Observed rotational and spin–orbit branching ratios are compared to the results of ab initio calculations. The differences between theory and experiment highlight the dominant role of rotational and spin–orbit interactions for the dynamic properties of the high‐nRydberg states involved in the pulsed field ionization process.