Abstract
Na 3 O has been generated by reacting preformed sodium clusters with O2 and N2O in a crossed beam pickup arrangement. This “superalkali” species was probed by photodepletion spectroscopy coupled with one-photon ionization mass spectroscopy to yield: (i) a first measure of visible/NIR region photodissociation cross sections showing several broad absorption features, (ii) a rough determination of the ground state dissociation energy (1.48±0.04 eV), as well as (iii) a remeasurement of the ionization potential (3.69±0.15 eV). The experimental investigations were supplemented by quantum chemical ab initio calculations employing coupled-cluster methods for ground and excited states of Na3O. Experiment and theory are in good agreement, allowing a tentative assignment of the Na3O depletion spectrum while providing further evidence for the computed D3h ground state. Observed and calculated dipole-allowed electronic transitions are discussed in terms of the unusual electronic structure of this nominally one excess-electron species.
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