A theoretical study of vibrational properties of neutral and cationic B 12 clusters

Calculations based on density functional theory predict the ground state of B 12 and B   + 12to be a convex planar configuration with C 1 symmetry. A small ionization‐induced structural change in B 12 is also predicted. It is suggested that multicentered bonds together with delocalized charge density are dominant factors in stabilizing the planar configuration over 3D configuration for B 12 and B   + 12 . The calculated vibrational frequencies lie in the range of 200–1328 cm −1 in which the high‐frequency modes are associated with asymmetric stretching of the boron atoms located at the cluster surface. The infrared spectra of both neutral and cationic B 12 show similar infrared active modes in the high‐frequency region, but different modes in the low‐frequency region due to dissimilar atomic charges in the cationic B 12 . The combined effect of charge delocalization and reduced dimensionality is reflected in the calculated static dipole polarizability of these clusters. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005