The Madelung Problem of Finite Crystals
Abstract
The Coulomb potential at an interior ion in a finite crystal of size p is given by a linear superposition of contributions from displacement vectors r = ( x, y, z ) to its neighbors. This additive structure underlies universal relationships among Madelung constants and applies to both standard periodic boundary conditions and alternative Clifford supercells. Each pairwise contribution decomposes into three physically distinct components: a periodic bulk term, a quadratic boundary term, and a finite-size correction, whose leading order term is [ 24 r 4 − 40 ( x 4 + y 4 + z 4 ) ] / [ 9 3 ( 2 p + 1 ) 2 ] for cubic crystals with unit lattice constant. Combining this decomposition with linear superposition yields a rapidly convergent direct-summation scheme, accurate even at p = 1 (3 3 unit cells), enabling hands-on calculations of Madelung constants for a wide range of ionic crystals.
Fields of Study & Subjects
High-pressure geophysics and materials
Quantum Mechanics and Non-Hermitian Physics
Electrostatics and Colloid Interactions
Publication details
- Journal / source
- Journal of Chemical Theory and Computation
- Publisher
- American Chemical Society (ACS)
- Volume
- 22
- Issue
- 6
- Pages
- 2790–2798
- Publication date
- 5 March 2026
- Language
- EN