Let be a stable equilibrium separation: , . With bond extension , the Taylor expansion is
The harmonic approximation applies when the typical thermal and zero-point bond fluctuations satisfy and the higher terms are negligible, for example and . The relevant small quantity is the relative displacement of neighbouring atoms. Small bond excursions about a stable minimum give an amplitude-independent spring constant . Large thermal excursions, bond breaking or appreciable anharmonicity invalidate the approximation.

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