In this work, we develop a new framework for computing atom-resolved contributions to optical properties based on atoms-in-molecules (AIM) schemes. The formalism is independent of the specific AIM method and is made rigorous by partitioning momentum matrix elements into atomic contributions while exactly satisfying the relevant sum rules. Zincblende GaP provides a two-atom demonstration of the atom-resolved second-harmonic-generation (SHG) analysis using five AIM partitioning methods. The two-center Ga-P channels account for $80.6\%–82.2\%$ of the SHG response, despite the pronounced partition dependence of the atomic charges. We then apply the framework to six representative ultraviolet nonlinear-optical crystals: $\beta \text{−}{\text{BaB}}_2{\text{O}}_4$ (BBO), ${\text{LiB}}_3{\text{O}}_5$ (LBO), ${\text{CsB}}_3{\text{O}}_5$ (CBO), ${\text{CsLiB}}_6{\text{O}}_{10}$ (CLBO), ${\text{KBe}}_2{\text{BO}}_3{\text{F}}_2$ (KBBF), and ${\text{LiCs}}_2{\text{PO}}_4$ (LCPO). The atom-triplet decomposition shows that two-center channels dominate the principal SHG components, while on-site terms are smaller and multicenter terms provide an important secondary contribution. Although the AIM charges, detailed local percentages, and exact pathway ranks depend on the partition, the physical interpretation remains stable across the tested AIM methods. B/O-only pathways dominate the leading responses of KBBF and LBO. Mixed pathways involving B/O or P/O atoms and cations make substantial contributions to the leading responses of BBO, CBO, CLBO, and LCPO. The decomposition framework therefore establishes a quantitative connection between local response pathways and the bulk nonlinear-optical response.

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• Electric polarization
• Electronic structure
• Microstructure
• Nonlinear optics
• First-principles calculations