CHAPTER NINE
Molecular Geometry and Bonding Theories
Molecular Shapes
Course: First
2013/2014
Lewis structures, do not indicate the shapes of molecules; they simply show the number and types of bonds. For example, the Lewis structure of CCl
4 tells us only that four Cl atoms are bonded to a central C atom:
The actual arrangement is the Cl atoms at the corners of a tetrahedron.
The shape of a molecule is determined by its bond angles , the angles made by the lines joining the nuclei of the atoms in the molecule.
The bond angles of a molecule, together with the bond lengths •(Section 8.8), define the shape and size of the molecule. In Figure 9.1, you should be able to see that there are six Cl-C-Cl bond angles in CCl
4
and that they all have the same value of 109.5° , the angle size characteristic of a tetrahedron. In addition, all four bonds are the same length (1.78 Ǻ).
Thus, the shape and size of CCl
4
are completely described by stating that the molecule is tetrahedral with bonds of length 1.78 Ǻ
.

Let us discuss the shape of molecules that have the general formula AB n ( in which the central atom A is bonded to n B atoms). The number of shapes possible for AB n molecules depends on the value of n .
The number of shapes possible for AB n molecules depends on the value of n . Those commonly found for AB
2
and AB
3
molecules are shown in _ FIGURE 9.2
. An AB2 molecule must be either linear (bond angle = 180° ) or bent (bond angle ≠ 180°) . For AB
3 molecules, the two most common shapes place the B atoms at the corners of an equilateral triangle. If the A atom lies in the same plane as the B atoms, the shape is trigonal planar . If the A atom lies above the plane of the B atoms, the shape is trigonal pyramidal
(a pyramid with an equilateral triangle as its base). Some AB3 molecules, such as ClF3, are T-shaped , the relatively unusual shape shown in Figure 9.2. The atoms lie in one plane, but the angles between them vary as shown.

We can predict the shapes of AB n
molecules using valence-shell electron-pair repulsion
(VSEPR) model ..
The VSEPR Model:

See Examples 9.1, 9.2, and 9.3
Covalent Bonding and Orbital Overlap:
The VSEPR model provides a simple means for predicting molecular geometries but does not explain why bonds exist between atoms.
According to valence-bond theory , the bonding electron pairs are concentrated in the regions between atoms and nonbonding electron pairs lie in directed regions of space.
In Lewis theory, covalent bonding occurs when atoms share electrons because the sharing concentrates electron density between the nuclei. In valence-bond theory, we visualize the buildup of electron density between two nuclei as occurring when a valence

atomic orbital of one atom shares space, or overlaps, with a valence atomic orbital of another atom. The overlap of orbitals allows two electrons of opposite spin to share the space between the nuclei, forming a covalent bond. Figure 9.13
(H
2
, HCl and Cl
2
molecules)
The covalent bond is formed when the orbitals overlap with each other, forming a concentrated electron density between the nuclei.
Hyprid Orbitals
The VSEPR model, is a simple model used for predicting molecular shape.
For example, based on the shapes and orientations of the 2 s and 2 p orbitals on a carbon atom, it is not obvious why a CH
4
molecule should have a tetrahedral geometry.
To explain molecular geometries, we can assume that the atomic orbitals on an atom (usually the central atom) mix to form new orbitals called hybrid orbitals . The shape of any hybrid orbital is different from the shapes of the original atomic orbitals. The process of mixing atomic orbitals is a mathematical operation called hybridization .
The total number of atomic orbitals on an atom remains constant, so the number of hybrid orbitals on an atom equals the number of atomic orbitals that are mixed. sp Hybrid orbitals consider the BeF 2 molecule, which has the Lewis structure:
F
Be F

The VSEPR model correctly predicts that BeF2 is linear with two identical Be ─ F bonds
The electron configuration of F is: (1 s
2
2 s
2
2 p
5
) indicates an unpaired electron in a 2 p orbital.
This electron can be paired with an unpaired Be electron to form a polar covalent bond.
The orbital diagram for a ground-state Be atom is
Because it has no unpaired electrons, the Be atom in its ground state cannot bond with the fluorine atoms. The Be atom could form two bonds, however, by “promoting” one of the 2 s electrons to a 2 p orbital:
Mixing the 2 s orbital with one 2 p orbital generate two new orbitals, hybrid orbitals as shown in FIGURE 9.15
. One s and one p orbital, we call each hybrid an sp hybrid orbital. According to the valence-bond model, a linear arrangement of electron domains implies sp hybridization .