Abstract
This chapter focuses on the main group elements beyond the second row of the periodic table. Beyond the second row of the periodic table, the elements become bigger and have more valence orbitals available; in particular, the existence of unoccupied valence d orbitals that are energetically accessible and able to take part in bonding provides substantial flexibility to the hybridization scheme and, hence, to bond angles. As a result, the balance between electronic and steric factors shifts in favor of the steric factors as one move beyond the second row. The consequence for predicting and systematizing geometries is that both the VSEPR and the AAIM methodologies work well in most instances. However, electronic factors are still important. In particular, it is still electronic factors that determine the number of ligands about the central atom. Electronic factors may also lead to orientationally-dependent bond strengths. In such cases, VSEPR is typically closer to the truth than the AAIM.
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