A Micromechanical Model for Light-interactive Molecular Crystals (2501.14975v1)

Abstract: Molecular crystals respond to a light stimulus by bending, twisting, rolling, jumping, or other kinematic behaviors. These behaviors are known to be affected by, among others, the intensity of the incident light, the aspect ratios of crystal geometries, and the volume changes accompanying phase transformation. While these factors, individually, explain the increase in internal energy of the system and its subsequent minimization through macroscopic deformation, they do not fully explain the diversity of deformations observed in molecular crystals. Here, we propose a micromechanical model based on the Cauchy-Born rule and photoreaction theory to predict the macroscopic response in molecular crystals. By accounting for lattice geometry changes and microstructural patterns that emerge during phase transformation, we predict a range of deformations in a representative molecular crystal (salicylideneamine). Doing so, we find that the interplay between photoexcited states and the energy minimization pathways, across a multi-well energy landscape, is crucial to the bending and twisting deformations. We use our model to analyze the role of particle geometries and the intensity of incident light on macroscopic deformation, and identify geometric regimes for shearing and twisting deformations in salicylideneamine crystals. Our micromechanical model is general and can be adapted to predict photomechanical deformation in other molecular crystals undergoing a solid-to-solid phase change and has potential as a computational design tool to engineer reversible and controllable actuation in molecular crystals.