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Sigma bond

physical science Maturity 11-13 Next article →

A sigma bond, or σ bond, is the strongest type of covalent chemical bond. These bonds form when atomic orbitals overlap in a head-on fashion. This specific type of overlap occurs along the internuclear axis, which is the straight line connecting two nuclei. Because the overlap is so direct, sigma bonds are very stable. The electrons involved in these bonds are often called sigma electrons.

Sigma bond
Sigma bond

To understand how they form, we must look at atomic orbitals. These are the regions where electrons exist around an atom. In a sigma bond, orbitals overlap directly along the axis between the atoms. When you look down this bond axis, the molecular orbital has circular symmetry. This symmetry makes it look similar to an "s" atomic orbital. Common ways these bonds form include s+s, pz+pz, s+pz, and dz2+dz2 overlaps. In these examples, "z" represents the internuclear axis.

Electron orbitals crop
Electron orbitals crop

Quantum theory adds another layer of complexity to how these bonds behave. It shows that molecular orbitals with identical symmetry can undergo a process called hybridization. This means the orbitals mix or blend together. For instance, the wavefunctions for s+s and pz+pz molecular orbitals can become blended. The extent of this hybridization depends on the relative energies of the molecular orbitals involved.

Molecular orbitals sq
Molecular orbitals sq

There is also a distinction between bonding and antibonding orbitals. For homonuclear diatomic molecules, bonding sigma orbitals have no nodal planes. A nodal plane is a location where the wavefunction is zero. However, an antibonding orbital, known as a sigma star orbital (σ*), is defined by having one nodal plane between the two bonded atoms.

Dihydrogen-LUMO-phase-3D-balls
Dihydrogen-LUMO-phase-3D-balls

Sigma bonds serve as the foundation for many different types of chemical structures. In a single bond, there is typically only one sigma bond. Multiple bonds are built using a sigma bond as a base combined with other bonds. A double bond consists of one sigma bond and one pi bond. A triple bond consists of one sigma bond and two pi bonds.

Molecular orbitals sq
Molecular orbitals sq

In complex organic molecules like propane, the structure is held together by many sigma bonds. Propane contains ten sigma bonds: two C−C bonds and eight C−H bonds.

Chemists use a specific formula to predict the number of sigma bonds in many molecules. This is known as the sigma bond rule. The formula is Nσ = Natoms + Nrings − 1. This rule is a special application of the Euler characteristic from graph theory. For a molecule with no rings, like ammonia (NH3), the number of bonds is simply the number of atoms minus one. For a molecule like anthracene (C14H10), which has three rings, the rule predicts 26 sigma bonds. This total includes 16 C−C bonds and 10 C−H bonds.

However, the sigma bond rule does not work for every molecular shape. It can fail for certain structures like Buckminsterfullerene (C60). While C60 has 60 atoms and 32 rings, it actually has 90 sigma bonds. The rule would incorrectly predict 91 bonds. This happens because the rule treats each ring as a face in a graph. In C60, the way the molecule is drawn can change how faces are counted. Other shapes, such as nanotubes or toroidal fullerenes, follow different mathematical patterns. For nanotubes, the number of sigma bonds is equal to the number of atoms plus the number of rings.

Molecular orbital of hydrogen fluoride
Molecular orbital of hydrogen fluoride
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🖼️ Images & Media (5)
File:Sigma bond.svg
Sigma bond.svg
File:Dihydrogen-LUMO-phase-3D-balls.png
Dihydrogen-LUMO-phase-3D-balls.png
File:Electron orbitals crop.svg
Electron orbitals crop.svg
File:Molecular orbitals sq.svg
Molecular orbitals sq.svg
File:Molecular orbital of hydrogen fluoride.svg
Molecular orbital of hydrogen fluoride.svg
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