Rotational branching ratios at low photoelectron energies in resonant enhanced multiphoton ionization of NO

Abstract

We report calculated rotational branching ratios for very low energy (50 meV) photoelectrons resulting from (1+1′) resonant enhanced multiphoton ionization (REMPI) via the J_i =1/2, 3/2, 5/2, and 7/2 levels of the P_(11) branch of the A ^2Σ^+ (3sσ) state of NO. Even angular momentum transfer (ΔN≡N_+−N_i) peaks are dominant in these rotational distributions, in agreement with the selection rule ΔN+l=odd. Angular momentum coupling in the photoelectron wave function arising from the molecular ion potential leads to smaller but appreciable ΔN=odd peaks. The calculated ΔN=0 to ΔN=+2 peak ratios show the same strong decrease when J_i increases from 1/2 to 3/2 as seen in the experimental zero‐kinetic‐energy (ZEKE) photoelectron spectra [Sander et al., Phys. Rev. A 36, 4543 (1987)], but do not show the rapid die‐off of the ΔN≠0 peaks for higher J_i observed experimentally. The calculated trend in the ΔN=+2 vs ΔN=0 peaks could be understood on the basis of simple angular momentum transfer arguments. These same arguments indicate that this trend in the ΔN=0 and +2 peaks with increasing angular momentum is not generally expected in other branches. Spectra via the R_(21) ( J) branch are presented to support this assertion. We also present photoelectron angular distributions which show a strong dependence on ΔN reflecting the changing composition of the photoelectron wave function.