Electronic structure and stability of Al n P n ( n = 2–4) clusters

The geometry, electronic configurations, harmonic vibrational frequencies, and stability of the structural isomers of aluminum phosphide clusters have been investigated using the density functional theory. For dimers and trimers, the lowest energy structures are cyclic (IIs, IIIs) with D nh symmetry. The caged structure with Td symmetry (Xs) lie lowest in energy among the tetramers. The AlP bond dominates the structures for many isomers so that one preferred dissociation channel is loss of the AlP monomer. The hybridization and chemical bonding in the different structures are also discussed. Comparisons with silicon and boron nitride clusters, the ground state structures of Al n P n clusters are analogous to those of their corresponding Si 2n counterparts. This similarity follows the isoelectronic principle. © 2004 Wiley Periodicals, Inc. J Comput Chem 26: 226–234, 2005