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The experiments were performed at the high-resolution beamline 10 of the Advanced Light Source. Effusive molecular beams were ionized by linearly polarized radiation. The photoelectron spectra were measured using a Scienta SES-200 hemispherical analyzer (46) at 54.7° with respect to the light polarization axis (eliminating angular effects) and were corrected afterward for spectrometer transmission. Because of the high performance of the analyzer, the vibrational lines were kept resolved throughout the photon energy range covered (22 to 60 eV). With negligible stray background, reliable areas proportional to the cross sections were extracted by summing the counts in a given kinetic energy window, avoiding systematic uncertainties attached to baselines coming from overlapping peaks and bypassing recourse to fitting with analytical line shapes. This was particularly important for these experiments because of the underlying rotational structure, almost resolved for the low v and responsible for asymmetric broadening for the high v.

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