Chain-End Reactivity and Anisotropic Electronic Softening Define Candidate Design Targets in BPDA/4,4'-ODA Polyimide Insulation.

Abstract

Identifying the molecular origins of thermal and electric-field response can guide polyimide insulation design. We combined an 18-film aromatic imide oligomer ensemble, reactive molecular dynamics, and signed finite-field r²SCAN-3c calculations to separate packing, chain-end chemistry, and directional electronic response. Independently initialized films exhibited a fivefold variation in probe-accessible volume, with distinct connected void geometries at similar accessible fractions. Across sixteen 5 ps thermal trajectories, terminal imide N-H sites accounted for 20 of 21 persistent reference-bond losses; the nonterminal inventory contained 14 new C-O connectivities and one C-N loss. In six matched film pairs, nonterminal records increased from 2 to 5 at 1600 K and from 12 to 19 at 1800 K between 5 and 10 ps, revealing the growing contribution of nonterminal rearrangement. Trajectories extending to 20 ps also resolved the onset of increased mass escape. At ±2 V nm^-1, the isolated ether-linked bis-imide fragment showed 0.342-0.841 eV frontier-gap narrowing across six directions, compared with at most 0.049 eV for the imide fragment, despite overlapping size-normalized induced responses. Together, these results identify chain termination and segment orientation as candidate design variables and provide quantitative descriptors for morphology-matched thermal comparisons and orientation-resolved electronic screening.