Morphology controls nonlinear donor acceptor thermodynamics in divinylbenzene-based copolymers.

Understanding how surface morphology governs molecular adsorption remains a fundamental challenge in interfacial science. Here, inverse gas chromatography at infinite dilution is combined with a generalized five-parameter Lewis acid-base model to investigate adsorption on divinylbenzene-based copolymers. Statistical model discrimination demonstrates that nonlinear donor-acceptor coupling and curvature are intrinsic features of polymer adsorption energetics. Independent thermo-geometric analysis further reveals that the adsorbed molecular footprint follows a common quadratic dependence on temperature and specific surface area, establishing a direct coupling between adsorption geometry and energetics. Quantitative correlations between geometric and energetic descriptors demonstrate that both originate from the same morphology-controlled interfacial field. These findings establish a unified thermodynamic framework in which specific surface area governs molecular packing and interaction strength, providing a predictive basis for understanding and engineering adsorption phenomena at heterogeneous polymer interfaces.