Chemical Origins of Non-Bonded Interactions Within and Between Solids

TL;DR

This paper introduces a generalized energy decomposition analysis to elucidate the chemical origins of non-bonded interactions in various solid-state materials, linking microscopic interactions to macroscopic properties.

Contribution

It extends localized molecular orbital analysis to solids, enabling interpretation of non-bonded interactions at the DFT level across diverse materials.

Findings

Dispersion influences polymorph stability in pharmaceuticals.

Stacking affects interlayer coupling in 2D materials.

Cation substitution alters quantum-well properties in layered perovskites.

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, moir\'e 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.