Structures and energetics of small lead cluster ions

Kelting, Rebecca; Otterstätter, Robin; Weis, Patrick; Drebov, Nedko; Ahlrichs, Reinhart; Kappes, Manfred M.
January 2011
Journal of Chemical Physics;1/14/2011, Vol. 134 Issue 2, p024311
Academic Journal
By a combination of gas phase ion mobility measurements and relativistic density functional theory calculations with inclusion of spin-orbit coupling, we assign structures of lead cluster cations and anions in the range between 4 and 15 atoms. We find a planar rhombus for the tetramer, a trigonal bipyramid for the pentamer, and a pentagonal bipyramid for the heptamer, independent of charge state. For the hexamer, the cation and anion structures differ: we find an octahedron for the anion while the cation consists of fused tetrahedra. For the octamer, we find in both cases structures based on the pentagonal bipyramid motif plus adatom. For the larger clusters investigated we always find different structures for cations and anions. For example, Pb12- is confirmed to be a hollow icosahedron while Pb12+ is a truncated filled icosahedron. Pb13+ is a filled icosahedron but Pb13- is a hollow icosahedron with the additional atom capping a face. In order to get experimental information on the relative stabilities, we investigated the collision induced dissociation mass spectra for the different cluster sizes and charge states, and observe a strong correlation with the calculated fragmentation energies. Up to n = 13 the main fragmentation channel is atom loss; for the larger cluster sizes we observe fission into two large fragments. This channel is dominant for larger anions, less pronounced but clearly present for the cations.


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