# Solid-State Energetics and Electrostatics: Madelung Constants and Madelung Energies

journal contribution

posted on 20.02.2012, 00:00 by Leslie GlasserThe Madelung constants of ionic solids relate to their
geometry
and electrostatic interactions. Furthermore, because of issues in
their evaluation, they are also of considerable mathematical interest.
The corresponding Madelung (electrostatic, coulomb) energy is the
principal contributor to the lattice energies of ionic systems, and
these energies largely influence many of their physical properties.
The Madelung constants are here defined and their properties considered.
A difficulty with their application is that they may be defined relative
to various lattice distances, and with various conventions for inclusion
of the charges, leading to possible confusion in their use. Instead,
the unambiguous Madelung energy,

*E*_{M}, is to be preferred in chemistry. An extensive list of Madelung energies is presented. From this data set, it is observed that there is a strong linear correlation between the lattice energies of ionic solids,*U*_{POT}, and their Madelung energies:*U*_{POT}/kJ mol^{–1}= 0.8519*E*_{M}+ 293.9. This correlation establishes that the lattice energy,*U*_{POT}, for ionic solids is about 15% smaller than the attractive Madelung energy, the difference arising from the repulsions unaccounted for by the solely coulombic Madelung energy calculation. Correlations of*U*_{POT}against*E*_{M}for alkali metal hydrides and transition metal compounds, each having considerable covalency, show much reduced Madelung contributions to the lattice energy. These correlations permit ready estimation of lattice energies, and are the first to be based on actual data rather than a broad analysis. The independent volume-based thermodynamic (VBT) method, which relies on a separate correlation with the formula unit volume of the ionic material, complements these correlations.