Ligand field theory

Article By:

Wentworth, R. A. D. Department of Chemistry, Indiana University, Bloomington, Indiana.

Last reviewed:January 2020

DOI:https://doi.org/10.1036/1097-8542.171400

An essentially ionic approach to chemical bonding which is often used with coordination compounds. These compounds consist of a central transition-metal ion that is surrounded by a regular array of coordinated atoms or ligands. Accordingcvcvly, the ligands are assumed to be sources of negative charge which perturb the energy levels of the central metal ion. In this respect the ligands subject the metal ion to an electric field which is analogous to the electric or crystal field produced by the regular distribution of nearest neighbors within an ionic crystalline lattice. For example, the crystal field produced by the Cl ion ligand in octahedral TiCl₆³⁻ is considered to be similar to that produced by the octahedral array of the six Cl ions about each Na ion in NaCl. The Na ion with its rare-gas configuration has an electronic charge distribution which is spherically symmetric both within and without the crystal field. The paramagnetic Ti(III) ion, which possesses one 3d electron (d¹), has a spherically symmetric charge distribution only in the absence of the crystal field produced by the ligands. The presence of the ligands destroys the spherical symmetry and produces a more complex set of energy levels within the central metal ion. The crystal field theory allows the energy levels to be calculated and related to experimental observation. See also: Coordination chemistry

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