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Results of combined theoretical and experimental studies of photoelectron spectra resulting from (2+1) resonance enhanced multiphoton ionization (REMPI) via the f ^1Π(3pσ), g ^1Δ(3pπ), and h ^1Σ^+(3pπ) Rydberg states of NH are reported. The overall agreement between these calculated and measured spectra is encouraging. Strong ΔN=N+−N’=even peaks, particularly for ΔN=0, are observed in these spectra. Low‐energy Cooper minima are predicted to occur in the l=2 wave of the kπ(^1Σ^+), kπ(^1Σ^−), and kπ(^1Δ) photoelectron channels for the f state, the kπ(^1Δ), kδ(^1Π), and kδ(^1Φ) channels for the g state, and the kπ(^1Σ^+) and kδ(^1Π) channels for the h state of NH. Depletion of the d wave (l=2) contributions to the photoelectron matrix element in the vicinity of these Cooper minima subsequently enhances the relative importance of the odd l  waves. The observed ΔN transitions are also affected by strong l  mixing in the electronic continuum induced by the nonspherical molecular potential. Interference of continuum waves between degenerate ionization channels also determines the spectral pattern observed for photoionization of the f ^1Π state of NH. Photoelectron angular distributions and the angular momentum compositions of photoelectron matrix elements provide further insight into the origin of these Cooper minima.

Rotationally resolved photoelectron spectra in resonance enhanced multiphoton ionization of Rydberg states of NH