Dimer-parity-dependent odd-even effects in photoinduced transitions to cholesteric and twist grain boundary smectic-C*mesophases: Experiments and simulations

We describe investigations on the influence of the flexible spacer parity and length of the guest photoactive liquid-crystalline dimers in guest-host mixtures exhibiting photoinduced transitions involving isotropic (I), cholesteric (N^{*}), and twist grain boundary smectic-C^{*} (TGBC^{*}) phases. Despite a small concentration (3 wt. %) of the guest molecules, the transition temperatures and their photodriven shift (δT) show a strong odd-even parity (of the dimer) dependent effect, with the even-parity systems having a larger value than their odd-parity counterparts; δT is larger for the N^{*}-TGBC^{*} transition than for the I-N^{*} one. The photocalorimetric measurements corroborate these features in addition to showing that, in comparison with the absence-of-ultraviolet (UV) case, the transition enthalpy (ΔH) of the I-N^{*} transition in the UV-on case is diminished by 33 and 12% for the mixtures with even- and odd-parity dimers, respectively. The duration for relaxation from the isothermal photodriven transition also exhibits general features of an odd-even influence. Molecular dynamics simulations demonstrate the presence of significant conformational heterogeneity and associated shift in the conformational space on photostimulation of the guest molecules. The change in the effective shape and nematic order parameter is more pronounced in the even-parity system.