# 9: Molecular Geometry and Bonding Theories

• 9.1: Molecular Shapes
The Lewis electron-pair approach described previously can be used to predict the number and types of bonds between the atoms in a substance, and it indicates which atoms have lone pairs of electrons. This approach gives no information about the actual arrangement of atoms in space, however.
• 9.2: The VSEPR Model
The VSEPR model can predict the structure of nearly any molecule or polyatomic ion in which the central atom is a nonmetal, as well as the structures of many molecules and polyatomic ions with a central metal atom. The VSEPR model is not a theory; it does not attempt to explain observations. Instead, it is a counting procedure that accurately predicts the three-dimensional structures of a large number of compounds, which cannot be predicted using the Lewis electron-pair approach.
• 9.3: Molecular Shape and Molecular Polarity
Compounds with polar covalent bonds have electrons that are shared unequally between the bonded atoms. The polarity of such a bond is determined largely by the relative electronegativites of the bonded atoms. The asymmetrical charge distribution in a polar substance produces a dipole moment, which is the product of the partial charges on the bonded atoms and the distance between them.
• 9.4: Covalent Bonding and Orbital Overlap
A more sophisticated treatment of bonding is needed for systems such as these. In this section, we present a quantum mechanical description of bonding, in which bonding electrons are viewed as being localized between the nuclei of the bonded atoms. The overlap of bonding orbitals is substantially increased through a process called hybridization, which results in the formation of stronger bonds.
• 9.5: Hybrid Orbitals
The localized valence bonding theory uses a process called hybridization, in which atomic orbitals that are similar in energy but not equivalent are combined mathematically to produce sets of equivalent orbitals that are properly oriented to form bonds. These new combinations are called hybrid atomic orbitals because they are produced by combining (hybridizing) two or more atomic orbitals from the same atom.
• 9.6: Multiple Bonds
To describe the bonding in more complex molecules with multiple bonds, we can use an approach that uses hybrid atomic orbitals to describe the $$\sigma$$ bonding and molecular orbitals to describe the $$\pi$$ bonding. In this approach, unhybridized np orbitals on atoms bonded to one another are allowed to interact to produce bonding, antibonding, or nonbonding combinations.
• 9.7: Molecular Orbitals
A molecular orbital is an allowed spatial distribution of electrons in a molecule that is associated with a particular orbital energy. Unlike an atomic orbital, which is centered on a single atom, a molecular orbital extends over all the atoms in a molecule or ion. Hence the molecular orbital theory of bonding is a delocalized approach. Molecular orbitals are constructed using linear combinations of atomic orbitals (LCAOs), which describe overlapping atomic orbitals.
• 9.8: Second-Row Diatomic Molecules
Molecular orbital energy-level diagrams for diatomic molecules can be created if the electron configuration of the parent atoms is known, following a few simple rules. Most important, the number of molecular orbitals in a molecule is the same as the number of atomic orbitals that interact. The difference between bonding and antibonding molecular orbital combinations is proportional to the overlap of the parent orbitals and decreases as the energy difference between the atomic orbitals increases.
• 9.E: Exercises
Problems and select solutions to the Chapter.
• 9.S: Molecular Geometry and Bonding Theories (Summary)