Valence Bond Theory - Practice Questions & MCQ

Valence bond theory describes a covalent bond as the overlap of half-filled atomic orbitals (each containing a single electron) that yield a pair of electrons shared between the two bonded atoms. We say that orbitals on two different atoms overlap when a portion of one orbital and a portion of a second orbital occupy the same region of space. According to valence bond theory, a covalent bond results when two conditions are met:

• An orbital on one atom overlaps an orbital on a second atom.

• The single electrons in each orbital combine to form an electron pair. 

The mutual attraction between these negatively charged electron pair and the two positively charged nuclei serves to physically link the two atoms through a force we define as a covalent bond. The strength of a covalent bond depends on the extent of overlap of the orbitals involved. Orbitals that overlap extensively form bonds that are stronger than those that have less overlap.

The energy of the system depends on how much the orbitals overlap. The figure given below shows how the sum of the energies of two hydrogen atoms (the colored curve) changes as they approach each other. When the atoms are far apart there is no overlap, and by convention we set the sum of the energies at zero. As the atoms move together, their orbitals begin to overlap. Each electron begins to feel the attraction of the nucleus in the other atom. In addition, the electrons begin to repel each other, as do the nuclei. While the atoms are still widely separated, the attractions are slightly stronger than the repulsions, and the energy of the system decreases. As the atoms move closer together, the overlap increases, so the attraction of the nuclei for the electrons continues to increase. At some specific distance between the atoms, which varies depending on the atoms involved, the energy reaches its lowest (most stable) value. This optimum distance between the two bonded nuclei is the bond distance between the two atoms. The bond is stable because at this point, the attractive and repulsive forces combine to create the lowest possible energy configuration. If the distance between the nuclei were to decrease further, the repulsion between nuclei and the repulsion between electrons would become stronger than the attractive forces and thus the energy of the system would then rise and leads the molecule unstable.

In addition to the distance between two orbitals, the orientation of orbitals also affects their overlap. Greater overlap is possible when orbitals are oriented such that they overlap on a direct line between the two nuclei. The figure given below shows this for two p orbitals from different atoms; the overlap is greater when the orbitals overlap end to end rather than at an angle.

(a) The overlap of two p orbitals is greatest when the orbitals are directed end to end. (b) Any other arrangement results in less overlap. The dots indicate the locations of the nuclei.

The overlap of two s orbitals, the overlap of an s orbital and a p orbital, and the end-to-end overlap of two p orbitals all produce sigma bonds (σ bonds), as given in the figure below. A σ bond is a covalent bond in which the electron density is concentrated in the region along the internuclear axis; that is, a line between the nuclei would pass through the center of the overlap region. Single bonds in Lewis structures are described as σ bonds in valence bond theory.

Sigma (σ) bonds form from the overlap of the following: (a) two s orbitals, (b) an s orbital and a p orbital, and (c) two p orbitals. 

A pi bond (π bond) is a type of covalent bond that results from the side-by-side overlap of two p orbitals. In a π bond, the regions of orbital overlap lie on opposite sides of the internuclear axis. Along the axis itself, there is a node, that is, a plane with no probability of finding an electron.

Pi (π) bonds form from the side-by-side overlap of two p orbitals. 

While all single bonds are σ bonds, multiple bonds consist of both σ and π bonds. As the Lewis structures below suggest, O2 contains a double bond, and N2 contains a triple bond. The double bond consists of one σ bond and one π bond, and the triple bond consists of one σ bond and two π bonds. Between any two atoms, the first bond formed will always be a σ bond, but there can only be one σ bond in any one location. In any multiple bond, there will be one σ bond, and the remaining one or two bonds will be π bonds.