Metal‐Metal Coordination Chemistry: Free Clusters of Group 12 Elements with Sodium

AbstractA systematic study of the mass spectra of particles formed in a supersonic nozzle expansion of Zn, Cd, and Hg vapors together with Na was performed. The particles discussed in this paper contain only one heavy atom and less than 12 Na ligands. Mass spectra from the neutral particles were generated by photoionization at five wavelengths (250, 260, 280, 300, and 320 nm) with a slit width corresponding to 16.5 and 3.3 nm, respectively. The abundances were corrected to relative differential ionization cross‐sections. Photoionization potentials for NanM with 5 <n< 10 and M = Zn, Cd, Hg were measured. Belown =6 no mixed clusters were found. The first abundance maximum occurred for all M atn= 8. A second maximum was withn= 16 orn= 18 (not covered in this paper). This selectivity can be rationalized by recent ab initio calculations by Fantucci et al. (J. Chem. Phys.; in press) and by jellium calculations, which give a closed shell atn =8 with the occupations 1s21p62s2. Ionization potentials clearly show a level reversal to 1p‐2s‐1d in contrast to the homonuclear jellium with 1p‐1d‐2s. This is similar to previous results with KnMg (Kappes, M. et al.,Chem. Phys. Lett., 1985,119