Pulsed field ionization (PFI) has been used in conjunction with a coherent vuv source to obtain high‐resolution threshold photoelectron spectra for the (000), (010), (020), and (100) vibrational states of the N2O+ cation. Simulations for the rotational profiles of each vibronic level were obtained by fitting the Buckingham–Orr–Sichel equations [A. D. Buckingham, B. J. Orr, and J. M. Sichel, Philos. Trans. R. Soc. London, Ser. A 268, 147 (1970)] using accurate spectroscopic constants for the ground states of the neutral and the ion. The relative branch intensities are interpreted in terms of the partial waves of the outgoing photoelectron to which the ionic core is coupled and in terms of the angular momentum transferred to the core. The PFI technique also allows us to report an improved value for the ionization potential of N2O of 103 963±5 cm−1.

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