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Walsh diagrams, often called angular coordinate diagrams or correlation diagrams, are representations of calculated orbital binding energies of a molecule versus a distortion coordinate , used for making quick predictions about the geometries of small molecules. By plotting the change in molecular orbital levels of a molecule as a function of geometrical change, Walsh diagrams explain why molecules are more stable in certain spatial configurations.
A major application of Walsh diagrams is to explain the regularity in structure observed for related molecules having identical numbers of valence electrons , and to account for how molecules alter their geometries as their number of electrons or spin state changes. Additionally, Walsh diagrams can be used to predict distortions of molecular geometry from knowledge of how the LUMO affects the HOMO when the molecule experiences geometrical perturbation.
Walsh's rule for predicting shapes of molecules states that a molecule will adopt a structure that best provides the most stability for its HOMO. If a particular structural change does not perturb the HOMO, the closest occupied molecular orbital governs the preference for geometrical orientation.