Jung-Hoon Yun

Photo-isomerization effect of the azobenzene chain on the opto-mechanical behavior of nematic polymer: A molecular dynamics study

The opto-mechanical properties of a photo-responsive nematic polymer network (PRPN) are investigated using molecular dynamics simulation. For the implementation of the trans-to-cis isomerization of azo compounds, a switchable potential formalism for the N = N bond is applied to the crosslinked PRPN unit cell model. During the light switch-on and heating-up simulations at a wide range of temperatures, the scalar orientational order parameter for the mesogenic side group molecules, the effective photo-induced strain of the bulk polymer network, and the opto-mechanical properties are characterized. The correlation between the microstate which belongs to the molecular location and the macroscopically observed photostrain is identified according to the isomerization ratio of the diazene groups.

Nonlinear photomechanics of nematic networks: upscaling microscopic behaviour to macroscopic deformation

A liquid crystal network whose chromophores are functionalized by photochromic dye exhibits light-induced mechanical behaviour. As a result, the micro-scaled thermotropic traits of the network and the macroscopic phase behaviour are both influenced as light alternates the shape of the dyes. In this paper, we present an analysis of this photomechanical behaviour based on the proposed multiscale framework, which incorporates the molecular details of microstate evolution into a continuum-based understanding. The effects of trans-to-cis photoisomerization driven by actinic light irradiation are first examined using molecular dynamics simulations, and are compared against the predictions of the classical dilution model; this reveals certain characteristics of mesogenic interaction upon isomerization, followed by changes in the polymeric structure. We then upscale the thermotropic phase-related information with the aid of a nonlinear finite element analysis; macroscopic deflection with respect to the wide ranges of temperature and actinic light intensity are thereby examined, which reveals that the classical model underestimates the true deformation. This work therefore provides measures for analysing photomechanics in general by bridging the gap between the micro- and macro-scales.

Molecular Dynamics Study on the Photothermal Actuation of a Glassy Photoresponsive Polymer Reinforced with Gold Nanoparticles with Size Effect.

We investigated the optical and thermal actuation behavior of densely cross-linked photoresponsive polymer (PRP) and polymer nanocomposites containing gold nanoparticles (PRP/Au) using all-atom molecular dynamics (MD) simulations. The modeled molecular structures contain a large number of photoreactive mesogens with linear orientation. Flexible side chains are interconnected through covalent bonds under periodic boundary conditions. A switchable dihedral potential was applied on a diazene moiety to describe the photochemical trans-to-cis isomerization. To quantify the photoinduced molecular reorientation and its effect on the macroscopic actuation of the neat PRP and PRP/Au materials, we characterized the photostrain and other material properties including elastic stiffness and thermal stability according to the photoisomerization ratio of the reactive groups. We particularly examined the effect of nanoparticle size on the photothermal actuation by varying the diameter of the nanofiller (10-20 Å) under the same volume fraction of 1.62%. The results indicated that the insertion of the gold nanoparticles enlarges the photostrain of the material while enhancing its mechanical stiffness and thermal stability. When the diameter of the nanoparticle reaches a size similar to or smaller than the length of the mesogen, the interfacial energy between the nanofiller and the surrounding polymer matrix does not significantly affect the alignment of the mesogens, but rather the adsorption energy at the interface generates a stable interphase layer. Hence, these improvements were more effective as the size of the gold nanoparticle decreased. The present findings suggest a wider analysis of the nanofiller-reinforced PRP composites and could be a guide for the mechanical design of the PRP actuator system.

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.