Chemical Origins of Non-Bonded Interactions Within and Between Solids

Abstract

Non-bonded interactions govern structure, stability, and function across a wide range of solid-state materials, yet their chemical origins are often difficult to resolve from total energies alone. Here we generalize absolutely localized molecular orbital energy decomposition analysis to quantify and interpret non-bonded interactions within and between solids at the density functional theory level. Across molecular crystals, moiré heterobilayers, and layered perovskite heterostructures, this framework separates lattice-formation energies, interlayer binding energies, and band-structure changes into chemically intuitive contributions from frozen interactions, polarization, and charge transfer. The analysis reveals how dispersion controls polymorph stability in pharmaceutical crystals, how local stacking modulates interlayer coupling in MoS2/WSe2, and how alkali-cation substitution switches the quantum-well character of layered perovskite heterostructures. By connecting emergent solid-state properties to microscopic interaction mechanisms, this framework provides a chemically transparent basis for understanding and designing complex materials.