Valence Bond Theory

Earlier we saw that covalent bonding requires the sharing of electrons between two atoms, so that each atom can complete its valence shell. But how does this sharing process occur? Remember that we can only estimate the likelihood of finding an electron in a certain area as a probability. This probability is represented as a distribution in space that we call an atomic orbital (Figure 1.3 “Representations of s and p atomic orbitals”)

Figure 1.3. Representations of s and p atomic orbitals.

The valence bond theory states that atoms in a covalent bond share electron density through the overlapping of their valence atomic orbitals. This creates an area of electron pair density between the two atoms. Since these electrons are simultaneously attracted to both nuclei, the electron pair holds the two atoms together.

Let’s examine the simplest case of atomic overlap resulting in a covalent bond, the formation of H₂ from two hydrogen atoms (Figure 1.1 “A diagram showing the overlap of s orbitals of two hydrogen atoms to form H₂“). The 1s orbitals of the two hydrogens approach each other and overlap to form a bond that has cylindrical symmetry known as a sigma bond (σ bond). Repulsion forces between the two nuclei and between the two electrons are also present. The optimal distance between atoms, which maximizes the attractive forces and minimizes the repulsive forces, gives the H-H sigma bond a length of 74 pm.

Figure 1.1. A diagram showing the overlap of s orbitals of two hydrogen atoms to form H₂.

For molecules that contain double or triple bonds, one of these bonds is a sigma bond, and the remaining multiple bonds are a different type of bond known as a pi bond (π bond). Pi bonds result from the sideways overlap of p orbitals, placing electron density on opposite sides of the internuclear axis (Figure 1.2 “Pi bond diagram showing sideways overlapping of p orbitals”).

Figure 1.2. Pi bond diagram showing sideways overlap of p orbitals.^[2]

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