Light penetration-coupled photoisomerization modeling for photodeformation of diarylethene single crystal: upscaling isomerization to macroscopic deformation

Diarylethene is one of the photo-responsive materials that show rapid and reversible changes in their color/electrochemical properties and macroscopic deformations in the crystalline phase by light irradiation. Photoisomerization is the main cause of the photo reactivity of diarylethene, and we established a statistical model based on the density matrix formalism, which predicts quantitative isomerization progress as a population term. The model reflects photo-switching properties of the target molecule, which were characterized by first principle calculations, and external stimulus factors (light irradiation conditions and temperature). By merging light penetration physics with the model, we derived light penetration depth dependent isomerization progress to theoretically investigate photodeformation of single crystal. The model well reproduced in-plane shear deformation under ultraviolet light irradiation which would provide guideline for photoactuator design. In addition, the statistical model addressed crucial findings (primary stimuli and molecular design parameter for increasing the isomerization rate, external stimuli enhancing fluorescence performance) itself.