Combined experimental and theoretical study of Al(n)X (n = 1-6; X = As, Sb) clusters: evidence of aromaticity and the Jellium model.
The electronic structure of Al(n)X (n = 1-6; X = As, Sb) clusters has been investigated using a synergistic approach combining negative ion photoelectron spectroscopy and first principles electronic structure calculations. It is shown that Al(3)X and Al(5)X exhibit enhanced energetic stability, as evidenced from calculated removal and embedding energies as well as chemical stability manifested through a large gap between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO). However, the stabilities of these species are derived from different mechanisms. Al(3)As and Al(3)Sb, with HOMO-LUMO gaps of 1.86 and 1.73 eV, respectively, are shown to have planar geometries where the p orbitals combine to form one pi and two sigma aromatic orbitals reminiscent of conventional all-metal aromatic species. Al(5)As and Al(5)Sb, with 20 valence electrons, possess a closed electronic shell (1s(2), 1p(6), 1d(10), 2s(2)) within a jellium framework and have HOMO-LUMO gaps of 1.12 and 1.17 eV, respectively.
Melko
Joshua J
JJ
Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, USA.
Clayborne
Peneé A
PA
Jones
Charles E
CE
Reveles
J Ulises
JU
Gupta
Ujjwal
U
Khanna
Shiv N
SN
Castleman
A W
AW