(2+1’) rotationally resolved resonance enhanced multiphoton ionization via the E ^2∑^+(4s,3d) and H ^2∑^+(3d,4s) Rydberg states of NO

The results of studies of ionic rotational branching ratios and photoelectron angular distributions resulting from (2+1’) resonance enhanced multiphoton ionization of NO via various high J (≊21.5) rotational branches of the E ^2∑^+(4s,3d) and H ^2∑^+(3d,4s) Rydberg states are presented. The rotational branching ratios show the expected ΔN=even rotational propensity rule with very small ΔN=odd signals. The branching ratios for the E ^2∑^+ state are seen to be independent of photoelectron energy with the ΔN=+2 signals strongest and no appreciable higher rotational transfer peaks (‖ΔN‖≥3). The higher rotational transfer signal for ionization of the H ^2∑^+ state are also negligible but the rotational branching ratios are strongly energy dependent due to a Cooper minimum in the l=3 partial wave of the kσ‐ and kπ‐continua at a photoelectron kinetic energy of 2.6 eV and 2.9 eV, respectively. This leads to a strong rotational selectivity that can be exploited to produce ions in a specific rotational level. These consequences of Cooper minima close to threshold are quite general and their influence on rotational distributions should be readily observable in other molecular systems. The photoelectron angular distributions via both states show a strong energy dependence with a rapid change in the angular distributions around the Cooper minimum associated with the H ^2∑^+ state