First-principles yet high-throughput screening of grafting-modified electronic structure in polymer insulator design

Polymer grafting is a strategic approach to modify its electrical performance for insulator applications. However, the graft effect on polymer electronic structure remains largely unexplored. Here, relying on first-principles simulation coupling classical molecular dynamics (MD), we introduce a high-throughput screening pipeline to compute grafting-modified electronic structure in amorphous phase, in order to identify the graft polymer suitable for high-performance insulators featuring shallow spatial charge trap, as exemplified by side chain engineering of graft polypropylene (PP), including hydroxyethyl methacrylate (HEMA), methyl methacrylate (MMA), and vinyl acetate (VAC). Despite the inevitable electron trap introduced by graft polar group, we find that these graft systems exhibit distinct trap depth and density, with VAC-grafted PP exhibiting the minimal spatial charge trap. And the electronic structure of these graft systems remains rarely altered under an electric field of working-level strength, ascribed to their overall nonpolar nature. Importantly, using small representative configurations from classical molecular dynamics, this first-principles screening pipeline is computationally efficient to execute in hours, enabling high-throughput computation for graft polymer insulator design.