Photoelectron Imaging and Density-Functional Investigation of Bismuth and Lead Anions Solvated in Ammonia Clusters

We present the results of photoelectron velocity-map imaging experiments for the photodetachment of small negatively charged ammonia solvated Bin and Pbn (n = 1, 2) clusters at 527 nm. The vertical detachment energies of the observed multiple electronic bands and their respective anisotropy parameters for the solvated Bi and Pb anions and clusters derived from the photoelectron images are reported. The electronic bands of Bi(NH3)n=1,2 are distinct from the Bi metal ion in exhibiting a perpendicular distribution whereas the electronic bands in Pb(NH3)n=1,2, unlike the Pb anion, show an isotropic distribution with respect to the laser polarization. Density-functional theory calculations with a generalized gradient approximation for the exchange−correlation potential were performed on these clusters to determine their atomic and electronic structures. Calculated geometries show a dramatic change between anionic and neutral ammonia solvated Bi and Pb species. Anionic clusters exhibit van der Waals interaction...