On the Effects of Different and Populations in Azobenzene Liquid Crystal Elastomers: A Monte Carlo Investigation.

We investigate main-chain liquid crystal elastomers (LCEs) formed by photoresponsive azobenzene units with different populations of and conformers (from fully to fully ). We study their macroscopic properties as well as their molecular organization using extensive Monte Carlo simulations of a simple coarse-grained model where the and conformers are represented by soft-core biaxial Gay-Berne particles with size and interaction energy parameters obtained by fitting a bare bone azobenzene moiety represented at atomistic level. We find that increasing the fraction of conformers, as could be obtained by near-UV irradiation, shifts the nematic-isotropic transition to a lower temperature, consistently with experiment, while generating internal stress in a clamped sample. An analysis of pair distributions shows that the immediate surroundings of a bent molecule are slightly less dense and more orientationally disordered in comparison with that of a conformer. Comparing nematic and smectic LCEs, actuation in the smectic phase proved less effective, disrupting the smectic layers to some extent but preserving orientational order of the azobenzene moieties.