Lanthanide contraction

Article By:

Spedding, Frank H. Formerly, Ames Laboratory, Energy Research and Development Administration, Iowa State University, Ames, Iowa.

Last reviewed:January 2020

DOI:https://doi.org/10.1036/1097-8542.370700

The name given to an unusual phenomenon encountered in the rare-earth series of elements. The radii of the atoms of the members of this series decrease slightly as the atomic number increases. Starting with element 58 in the periodic table, the balancing electron fills in an inner incomplete 4f shell as the charge on the nucleus increases. According to the theory of atomic structure, this shell can hold 14 electrons; so starting with element 58, cerium, there are 14 true rare earths. Lanthanum has no electrons in the 4f shell, cerium has 1, and lutetium, 14. The 4f electrons play almost no role in chemical valence; therefore, all rare earths can have three electrons in their valence shell and they all exist as trivalent ions in solution. As the charge on the nucleus increases across the rare-earth series, all electrons are pulled in closer to the nucleus so that the radii of the rare-earth ions decrease slightly as the compounds go across the rare-earth series. Any given compound of the rare earths is very likely to crystallize with the same structure as any other rare earth. However, the lattice parameters become smaller and the crystal denser as the compound proceed across the series. This contraction of the lattice parameters is known as the lanthanide contraction. For many compounds the lattice parameters decrease only partway across the series, and when the contraction has progressed to that point, a new crystalline form develops. Frequently, both crystalline forms can be observed for a number of the elements. For this reason, the rare-earth series is of particular interest to scientists because many of the parameters determining the properties of a substance can be kept constant while the lattice spacings can be varied in small increments across the series.

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