Photoelectron spectroscopy of negatively charged bismuth clusters: Bi−2, Bi−3, and Bi−4

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Abstract
We have recorded the 351 nm photoelectron spectra of Bi−2, Bi−3, and Bi−4. The spectrum of Bi−2 shows transitions to at least seven electronic states of Bi2 neutral, four of which are observed with vibrational resolution. Term energies, bond lengths, and vibrational frequencies are obtained for the anion ground state and for the first three excited states of Bi2. These results are compared to previous spectroscopic measurements and to the ab initio calculations presented in the accompanying paper. The photoelectron spectrum of Bi−3 reveals some of the electronic structure of Bi3 and the results are discussed in comparison to recent theoretical work. Adiabatic electron affinities are obtained for Bi2 [1.271(8) eV] and for Bi3 [1.60(3) eV]. The electron affinity of Bi4 is estimated from the onset of photodetachment to be 1.05(10) eV.