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Chemistry · Ch 10 — Chemical Bonding

Sigma and Pi Bonds

10.8.1

Sigma and Pi Bonds

Sigma (σ) bond. When two atomic orbitals overlap LINEARLY, along the axis joining the two nuclei, the resulting bond is a sigma bond -- also called 'head-on overlap' or 'axial overlap'. Any overlap that involves an s orbital (i.e. s-s or s-p overlap) ALWAYS results in a sigma bond, because the s orbital is spherically symmetric and so overlaps head-on no matter the direction of approach. Overlap between two p orbitals ALONG the molecular axis also gives a sigma bond -- for instance, if the x-axis is taken as the molecular axis, then a pₓ-pₓ overlap results in a σ bond.

Pi (π) bond. When two atomic orbitals overlap SIDEWAYS (laterally) -- their lobes lying parallel to each other but perpendicular to the internuclear axis -- the resulting covalent bond is a pi bond. Taking the x-axis as the molecular axis, p_y-p_y and p_z-p_z overlaps (both perpendicular to x) result in π-bond formation. …