The results of a zero‐kinetic‐energy pulsed‐field ionization study on the a 1Δ (v+=0) excited ionic state of SH+ (SD+) obtained via two‐photon excitation of the [a 1Δ]3dπ 2Φ (v′=0) Rydberg state and subsequent one‐photon pulsed‐field ionization are reported. Accurate ionization energies as well as rotational constants are obtained. A detailed comparison between the rotational branching ratios resulting from the pulsed‐field ionization process and those of a direct ionization process is made. The results elucidate the dynamics of the high‐n Rydberg states involved in pulsed‐field ionization of SH (SD).
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