The A 2Σ+ state of rare gas–NO van der Waals molecules probed by 1+1 multiphoton ionization spectroscopy

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Abstract
The previously unobserved bound–bound spectra of ArNO, KrNO, and XeNO have been observed slightly blue shifted from the (1,0) and (0,0) bands of the A 2Σ+←X 2Π1 / 2 transition of uncomplexed nitric oxide. Although the structured but incomplete spectra cannot be assigned with certainty, limits to the ground and excited state bond dissociation energies,D ‘ 0 and D 0, respectively, can be estimated. For ArNO these limits are D ‘ 0 ≥89 and 54 cm− 1≤D 0 ≤101 cm− 1. The observed fragmentation of the KrNO and XeNO molecules, coupled with earlier results for MPI via the C 2Π state, suggests that superexcited, autoionizing states of the van der Waals molecules dissociate to yield excited rare gas atoms whenever energetically possible.