A (2+1) resonance-enhanced multiphoton ionization–photoelectron spectroscopy (REMPI-PES) study of the OH radical has been carried out in the two-photon energy region between 81 300 and 88 900 cm−1. Translationally and rotationally hot OH radicals are generated via photodissociation of hydrogen peroxide or formic acid. The known D 2Σ− (v′=0–2) and hitherto unobserved 3 2Σ−(v′=0) intermediate states in this region (at 81 815.8 and 87 643.7 cm−1 above the ground state) are shown to possess predominant Rydberg character. From the rotational structure in the REMPI spectrum physical parameters have been derived for these states.

A (2 + 1) REMPI-PES study of HCI has been carried out in t h e two-photon energy region between 77000 a n d 85500 cm-'. The observed 'A(2), 'A(2), 'II(l) and 'X-(O+) states are characterized as Rydberg states. The one-photon ionization of t h e B 'X+ state has been shown to be dominated by indirect processes involving competition between electronic autoionization and dissociation via superexcited states.

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