Bending Ternary Dihalides.

Abstract

The bonding preferences in the mixed dihalides (MXY) of groups 2 and 12 metals, including the extent of any anomalous bending, are assessed and established. The deviation from linearity in group 2 metal binary dihalides is well-known, runs contrary to simple bonding models, and is believed to be decisive for structural preferences in the extended solids. Yet the bonding in the ternary, MXY, molecules has not been investigated systematically until now. The structure and bonding in these ternary systems (and, for completeness, the binary cases as well) are determined herein at high levels of theory. A softness criterion formulated by Szentpály and Schwerdtfeger, and tested initially on binary dihalides with predictions for mixed systems, is confirmed to apply broadly for binary and ternary species of the group 2 and 12 metals. For each M, a function of the form E(Θ) = Ae- kΘ is shown to predict the barriers to linearization for all of the bent molecules. The extended solids of some of the ternary dihalides are of interest for their optical properties. The bonding in the molecular (MXY) units may offer we think some new perspectives from which to rationalize the bonding preferences in those crystal structures.