Computational Assessment of Atom Transfer Radical Polymerization in Thermosensitive Poly(Ethylene‐Glycol)‐block‐Poly((2‐(Dimethylamino)Ethyl‐Methacrylate) Copolymer

Abstract Molecular modeling currently plays an important role in chemistry, providing predictions about the structure and properties of chemical compounds in the design and development of new materials. Herein, the thermosensitive block copolymer poly(ethylene‐glycol)‐block‐poly((2‐dimethylamino)ethyl methacrylate) (PEG‐ b ‐PDMAEMA) was synthesized using atom transfer radical polymerization (ATRP). The structural properties and energy species of the polymer have been evaluated through theoretical studies using density functional theory (DFT). In particular, the electronic properties of the polymers, based on the composition of methacrylate monomers, have been evaluated through the HOMO‐LUMO gap energy, which allows for the description of the global chemical reactivity of the molecules. The electrostatic potential map of the polymer indicates that the oxygen and nitrogen atoms of the PEG‐ b ‐PDMAEMA polymer are the most effective sites for intermolecular interactions. The nature of interactions in polymer molecules, including steric repulsion, hydrogen bonding, and Van der Waals interactions, was analyzed using the Reduced Density Gradient (RDG) method.