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Chemistry · Glossary

What is σ and π orbitals?

Also known as: sigma orbital · pi orbital

Definition 14.6 University Chemistry — Year 2 · Chapter 14 — Molecular Orbitals of Diatomic Molecules

A σ\sigma orbital of a linear molecule is unchanged by any rotation about the molecular axis: it has no nodal plane containing the axis. A π\pi orbital changes sign under a rotation of 180∘180^\circ about the axis: it has one nodal plane containing the axis. An asterisk marks antibonding orbitals (σ∗\sigma^*, π∗\pi^*).

Molecular orbitals of a homonuclear diatomic, schematic (the molecular axis is horizontal and dashed). In-phase combinations (bonding) gather the same colour between the nuclei; out-of-phase combinations (antibonding) put a nodal plane between them.  orbitals are symmetric about the axis; each π orbital has the axis in its nodal plane.
Molecular orbitals of a homonuclear diatomic, schematic (the molecular axis is horizontal and dashed). In-phase combinations (bonding) gather the same colour between the nuclei; out-of-phase combinations (antibonding) put a nodal plane between them. σ\sigma orbitals are symmetric about the axis; each π\pi orbital has the axis in its nodal plane.
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