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This paper reports the comparison of experimental photoionisation spectra of deuterated ammonia (ND3), previously recorded by (1+1′) two-photon excitation via the B state (v2′=5,6) S. Kuijpers, P. Kalaitzis, E. Sakkoula, S. van de Meerakker, T. Softley and D. Parker, J. Phys. Chem. 128, 10993–11004 (2024)., with multichannel quantum defect theory (MQDT) simulations. The spectra show a dense Rydberg structure which is analysed in terms of over 20 different Rydberg series in each case. New experimental spectra, recorded via the B-state v2′=7 intermediate, and a 2+1′ photoionisation spectrum recorded via v2′=5 are also reported here, and MQDT simulations are presented. Using the same quantum defect parameters, the rotationally resolved photoelectron spectra (PES) with 1+1′ excitation via v2′=6 reported in Reference S. Kuijpers et al. are also simulated with MQDT, and show a satisfying level of agreement with experiment. The calculations provide a verification of qualitative arguments about the relative propensity for autoionizing into a range of available open channels, and also an explanation for the differences between PES measured at a resonant wavelength (on a peak in the photoionisation spectrum) as opposed to those recorded off-resonance.
Kuijpers et al. (Sat,) studied this question.