ligand field theory

▪ chemistry

      in chemistry, one of several theories that describe the electronic structure of coordination or complex compounds, notably transition metal complexes, which consist of a central metal atom surrounded by a group of electron-rich atoms or molecules called ligands. The ligand field theory deals with the origins and consequences of metal– ligand interactions as a means of elucidating the magnetic, optical, and chemical properties of these compounds.

      Attributed mainly to the works of the U.S. physicist J.H. Van Vleck (Van Vleck, John H.), the ligand field theory evolved from the earlier crystal field theory, developed for crystalline solids by the U.S. physicist Hans Albrecht Bethe (Bethe, Hans). Bethe's theory considers the metal–ligand linkage as a purely ionic bond; i.e., the bond between two particles of opposite electrical charges. It further assumes that the electronic structure of the metal atom is altered by the electrical field generated by the surrounding negative charges (the ligand field). In particular, the effects of the ligand field on the five d orbitals (orbital) of an inner electron shell of the central atom are considered. (The d orbitals are regions within an electron shell with certain preferred orientations in space; in transition metals these orbitals are only partly occupied by electrons.) In the isolated metal atom, the d orbitals are of the same energy state and have equal probabilities of being occupied by electrons. In the presence of the ligand field these orbitals may be split into two or more groups that differ slightly in energy; the manner and the extent of orbital splitting depend on the geometric arrangement of the ligands with respect to the orbitals and on the strength of the ligand field.

      The change in energy state is accompanied by a redistribution of electrons; in the extreme, those orbitals promoted to a higher energy state may be left unoccupied, and those orbitals brought to a lower energy state may become completely filled by pairs of electrons with opposite spin. Molecules that contain unpaired electrons are attracted to a magnet and are called paramagnetic; the state of pairing or unpairing of electrons in metal complexes is correctly predicted from the concept of orbital splitting. The colours of metal complexes are also explained in terms of the split d orbitals: because the energy differences among these orbitals are comparatively small, electronic transitions are readily achieved by absorption of radiation in the visible range.

      The ligand field theory goes beyond the crystal field theory, however. The chemical bond between the metal and the ligands and the origins of orbital splitting are ascribed not only to electrostatic forces but also to a small degree of overlap of metal and ligand orbitals and a delocalization of metal and ligand electrons. Introduction of these modifications into the quantum-mechanical formulation of the crystal field theory improves the agreement of its quantitative predictions with experimental observations. In another theory, called the molecular orbital theory—also applied to coordination compounds—complete mixing of metal and ligand orbitals (to form molecular orbitals) and complete delocalization of electrons are assumed.

      In some contexts, the term ligand field theory is used as a general name for the whole gradation of theories from the crystal field theory to the molecular orbital theory.

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