Abstract
Recent photoelectron spectroscopic studies in a (2 + 1) REMPI of NO via the Rydberg D 2Σ + state have revealed anomalous ionic rotational branching ratios. We have performed ab initio calculations of these branching ratios and find that the molecular nature of the ionization continuum plays an essential role in the dynamics. Even though the bound orbital is very atomic-like (⪢ 98% p-like), the photoelectron continuum wavefunction is quite sensitive to the non-spherical nature of the molecular ionic potential and causes a strong persistence of the p-partial wave which, in turn, leads to a large Δ N = 0 peak.
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