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Molecular Geometry and Electron Domain Theory

Author: John Hutchinson

We begin by assuming a Lewis structure model for chemical bonding based on valence shell electron pair sharing and the octet rule. We thus assume the nuclear structure of the atom, and we further assume the existence of a valence shell of electrons in each atom which dominates the chemical behavior of that atom. A covalent chemical bond is formed when the two bonded atoms share a pair of valence shell electrons between them. In general, atoms of Groups IV through VII bond so as to complete an octet of valence shell electrons. A number of atoms, including C, N, O, P, and S, can form double or triple bonds as needed to complete an octet. We know that double bonds are generally stronger and have shorter lengths than single bonds, and triple bonds are stronger and shorter than double bonds.

We should expect that the properties of molecules, and correspondingly the substances which they comprise, should depend on the details of the structure and bonding in these molecules. The relationship between bonding, structure, and properties is comparatively simple in diatomic molecules, which contain two atoms only, e.g. HCl or O2. A polyatomic molecule contains more than two atoms. An example of the complexities which arise with polyatomic molecules is molecular geometry: how are the atoms in the molecule arranged with respect to one another? In a diatomic molecule, only a single molecular geometry is possible since the two atoms must lie on a line. However, with a triatomic molecule (three atoms), there are two possible geometries: the atoms may lie on a line, producing a linear molecule, or not, producing a bent molecule. In molecules with more than three atoms, there are many more possible geometries. What geometries are actually observed? What determines which geometry will be observed in a particular molecule? We seek a model which allows us to understand the observed geometries of molecules and thus to predict these geometries.

Once we have developed an understanding of the relationship between molecular structure and chemical bonding, we can attempt an understanding of the relationship of the structure and bonding in a polyatomic molecule to the physical and chemical properties we observe for those molecules.

Last Update: 2011-04-08