Mechanical Effect Produced by Photo‐Switchable Reactions: Insights from Molecular Simulations

Light‐responsive shape‐changing polymers are photonastic materials: they can convert light into mechanical energy through macroscopic transformations. Indeed, photochromic molecules embedded in these polymer films present light‐induced structural modifications that can trigger a significant macroscopic deformation. In this theoretical study based on molecular dynamics simulations, analysis tools ranging from atomic to supramolecular scales are developed to investigate this photonastic phenomenon. To this purpose, a model system built upon an azobenzene photochrome embedded in different environments (tetrahydrofuran, cis‐1,4‐polybutadiene and hydroxyl‐terminated polybutadiene) is considered. First, the impact of the environment on the photochrome properties is discussed through the analysis of the structural properties, ultra‐violet visible (UV–vis) absorption spectra and dynamical properties of the photoswitch. Then, the impact of the presence of the photochrome on the polymer is studied. At the atomic scale, the radial distribution functions show some differences between the cis and trans isomers due to geometrical effects. At the molecular scale, the analysis of the size and shape of the polymer chains reveals that the photochrome has no impact on the chain properties. Finally, at the macroscopic scale, the cohesive energy density shows that the polymer is stabilized by the presence of photochrome molecules. Light‐responsive shape‐changing polymers can convert light into mechanical energy through macroscopic transformations. In this theoretical study based on molecular dynamics simulations and time‐dependent density functional theory calculations, analysis tools ranging from atomic to supramolecular scales are developed to investigate this phenomenon for a model system built upon an azobenzene photochrome embedded in different environments (tetrahydrofuran, cis‐1,4‐polybutadiene and hydroxyl‐terminated polybutadiene).