Jahn–Teller effect

The Jahn–Teller effect (JT effect or JTE) is an important mechanism of spontaneous symmetry breaking in molecular and solid-state systems which has far-reaching consequences for different fields, and it is related to a variety of applications in spectroscopy, stereochemistry and crystal chemistry, molecular and solid-state physics, and materials science.

The Jahn–Teller effect, sometimes also known as Jahn–Teller distortion, describes the geometrical distortion of molecules and ions that is associated with certain electron configurations. The Jahn–Teller theorem essentially states that any nonlinear molecule with a spatially degenerate electronic ground state will undergo a geometrical distortion that removes that degeneracy, because the distortion lowers the overall energy of the species. For a description of another type of geometrical distortion that occurs in crystals with substitutional impurities see article off-center ions.

The Jahn–Teller effect is most often encountered in octahedral complexes of the transition metals. The phenomenon is very common in six-coordinate copper(II) complexes. The d⁹ electronic configuration of this ion gives three electrons in the two degenerate e_g orbitals, leading to a doubly degenerate electronic ground state. Such complexes distort along one of the molecular fourfold axes (always labelled the z axis), which has the effect of removing the orbital and electronic degeneracies and lowering the overall energy. The distortion normally takes the form of elongating the bonds to the ligands lying along the z axis, but occasionally occurs as a shortening of these bonds instead (the Jahn–Teller theorem does not predict the direction of the distortion, only the presence of an unstable geometry). When such an elongation occurs, the effect is to lower the electrostatic repulsion between the electron-pair on the Lewis basic ligand and any electrons in orbitals with a z component, thus lowering the energy of the complex. Inversion centre is preserved after the distortion.

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