Heteronuclear and Homonuclear High-Spin Alkali Trimers on Helium Nanodroplets

The electronic excitation spectra of all possible homo- and heteronuclear high-spin (quartet) trimers of K and Rb (K_xRb_3-x, x=0…3) assembled on the surface of superfluid helium droplets, are measured in the spectral range from 10 600 to 17 400  cm^-1. A regular series of corresponding bands is observed, reflecting the similar electronic structure of all these trimers. For the assignment and separation of overlapping bands, we determine x directly, with mass-selected beam depletion, and indirectly with a V-type double-resonance scheme. The assignment is confirmed by high-level ab initio calculations of the electronic structure of the bare trimers. The level structure is rationalized in terms of harmonic-oscillator states of the three valence electrons in a quantum-dot-like confining potential. We predict that three should be a magic number for high-spin alkali clusters.