RESONANCE-ENHANCED MULTIPHOTON IONIZATION SPECTROSCOPY OF THE NH(ND) RADICAL .1. THE D-1-SIGMA+ STATE

The d 1-SIGMA+ state, previously identified in emission, is confirmed as being the state responsible for the two-photon resonance enhancement in the MPI spectrum of a 1-DELTA state imidogen radicals at excitation wavelengths around 285 nm. We present the first reliable estimate of the bond-dissociation energy of this excited state. Two-photon resonant MPI via the d state is observed to yield both parent NH+ (ND+) and atomic, N+ and H+(D+), ions. Three possible mechanisms for fragment ion formation are considered. Four-photon ionisation doubly resonance-enhanced, first (at the two-photon energy) by levels of the 1-SIGMA+ state and then (at the three-photon energy) by autoionising members of the Rydberg series converging to one or more of the excited ionisation limits, is considered best able to explain the substantially enhanced N+ ion yields observed when MPI occurs via a select subset of the d-a resonances. Parallels between the ionisation behaviour found in this present investigation and that seen in previous studies of two-photon resonant MPI of b 1-SIGMA+ state PH(PD) radicals suggest the need for a reassignment of the resonance-enhancing excited state of PH(PD).