10.5
Valence bond theory is one method used to understand how the atomic orbitals from the quantum mechanical model can overlap to produce a covalent bond. It assumes that bonds form when atomic interactions lower the overall energy of the system.
Consider the formation of a hydrogen molecule. Each atom has a single electron in its 1s orbital. When far apart, the hydrogen atoms do not experience either attraction to or repulsion from each other, and the energy of the system is considered to be zero.
As the atoms move closer to each other, each electron feels the attraction of the nucleus in the other atom. At the same time, the electrons repel each other, as do the nuclei.
If the attractions are stronger than the repulsions, the energy of the system decreases as the atoms approach each other. The minimum potential energy is reached when the electron-electron and nucleus-nucleus repulsions balance the attractive forces between electrons and nuclei.
For hydrogen molecules, this occurs when the bond length is 74 picometers. At this point, a substantial overlap of the two hydrogen 1s orbitals occurs and forms a covalent bond. The two electrons with opposite spins are attracted to both the nuclei and lie in the space shared by both atomic orbitals.
If the internuclear distance is reduced further, the energy begins to rise, mainly due to the electrostatic repulsion between the nuclei.
Valence bond theory proposes that a chemical bond results through an overlap of partially filled atomic orbitals, including those other than spherical s orbital.
In hydrogen fluoride, the half-filled 1s orbital from hydrogen and the half-filled 2p orbital of fluorine can interact. The p orbital lies along the internuclear axis, and overlaps with the s orbital from hydrogen forming a bond.
When a single bond forms between two non-spherical orbitals, the two orbitals will have the head-to-head overlap. The covalent bond in a fluorine molecule is formed from the overlap of two half-filled p orbitals ensuring the maximal overlap and a stronger bond.
The type covalent bond formed by head-to-head overlap of atomic orbitals is called a sigma (σ) bond.
Valence bond theory describes a covalent bond as the overlap of half-filled atomic orbitals (each containing a single…
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