Understanding Trends in Molecular Bond Angles.

Abstract

Trends in bond angle are identified in a systematic study of more than a thousand symmetric A2B triatomic molecules. We show that, in series where atoms A and B are each varied within a group, the following trends hold: (1) the A–B–A bond angle decreases for more polarizable central atoms B, and (2) the A–B–A angle increases for more polarizable outer atoms A. The physical underpinning is provided by the extended Debye polarizability model for the chemical bond angle, hence our present findings also serve as validation of this simple classical model. We use experimental bond angles from the literature and, where not available, we optimize molecular geometries with quantum chemical methods, with an open mind with regards to the stability of these molecules. We consider main group elements up to and including the sixth period of the periodic table.