Comment on "Electronic, vibrational and torsional couplings in N-methylpyrrole: Ground, first excited and cation states" [J. Chem. Phys. 154, 224305 (2021)].

Two-color (1 + 1′) zero-electron-kinetic-energy (ZEKE) and photoionization efficiency (PIE) spectra are reported via different levels in the S1 ← S0 ( A ̃ 1 A 2 ← X ̃ 1 A 1 ) one-photon transition of jet-cooled N-methylpyrrole. The laser radiation is produced using two dye lasers, one with an 1800 l/mm grating and one with 2400 l/mm. We report spectra where the excitation and ionization radiation are produced with both combinations of the dye lasers; these spectra differ markedly. This is attributed to Wood's anomalies with the 2400 l/mm grating: one aspect is a loss in light intensity over a range of wavelengths, attributed to a resonance anomaly. Another is the appearance of a "shadow" ZEKE spectrum and PIE curve at apparently higher ionization wavenumbers; under some conditions, a third ZEKE spectrum was observed—these latter observations arise from higher-order dispersion effects, likely caused by a Rayleigh anomaly. We comment on these observations and report more representative ZEKE and PIE spectra than those presented in a recent paper by our group [A. R. Davies, D. J. Kemp, and T. G. Wright, J. Chem. Phys. 154, 224305 (2021)] for four intermediate S1 levels. [ABSTRACT FROM AUTHOR]