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Concept
Sigma bond
Summary
In chemistry, sigma bonds (σ bonds) are the strongest type of covalent chemical bond. They are formed by head-on overlapping between atomic orbitals. Sigma bonding is most simply defined for diatomic molecules using the language and tools of symmetry groups. In this formal approach, a σ-bond is symmetrical with respect to rotation about the bond axis. By this definition, common forms of sigma bonds are s+s, pz+pz, s+pz and dz2+dz2 (where z is defined as the axis of the bond or the internuclear axis).
Quantum theory also indicates that molecular orbitals (MO) of identical symmetry actually mix or hybridize. As a practical consequence of this mixing of diatomic molecules, the wavefunctions s+s and pz+pz molecular orbitals become blended. The extent of this mixing (or hybridization or blending) depends on the relative energies of the MOs of like symmetry.
For homodiatomics (homonuclear diatomic molecules), bonding σ orbitals have no nodal planes at which the wavefunction is zero, either between the bonded atoms or passing through the bonded atoms. The corresponding antibonding, or σ* orbital, is defined by the presence of one nodal plane between the two bonded atoms.
Sigma bonds are the strongest type of covalent bonds due to the direct overlap of orbitals, and the electrons in these bonds are sometimes referred to as sigma electrons.
The symbol σ is the Greek letter sigma. When viewed down the bond axis, a σ MO has a circular symmetry, hence resembling a similarly sounding "s" atomic orbital.
Typically, a single bond is a sigma bond while a multiple bond is composed of one sigma bond together with pi or other bonds. A double bond has one sigma plus one pi bond, and a triple bond has one sigma plus two pi bonds.
Sigma bonds are obtained by head-on overlapping of atomic orbitals. The concept of sigma bonding is extended to describe bonding interactions involving overlap of a single lobe of one orbital with a single lobe of another. For example, propane is described as consisting of ten sigma bonds, one each for the two C−C bonds and one each for the eight C−H bonds.
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