de Vries behavior of the electroclinic effect in the smectic-A* phase near a biaxiality-induced smectic-A*-smectic-C* tricritical point

Using a generalized Landau theory involving orientational, layering, tilt, and biaxial order parameters we analyze the smectic-A* and smectic-C* (Sm-A*-Sm-C*) transitions, showing that a combination of small orientational order and large layering order leads to Sm-A*-Sm-C* transitions that are either continuous and close to tricriticality or first order. The model predicts that in such systems the increase in birefringence upon entry to the Sm-C* phase will be especially rapid. It also predicts that the change in layer spacing at the Sm-A*-Sm-C* transition will be proportional to the orientational order. These are two hallmarks of Sm-A*-Sm-C* transitions in de Vries materials. We analyze the electroclinic effect in the Sm-A* phase and show that as a result of the zero-field Sm-A*-Sm-C* transition being either continuous and close to tricriticality or first order (i.e., for systems with a combination of weak orientational order and strong layering order), the electroclinic response of the tilt will be unusually strong. Additionally, we investigate the associated electrically induced change in birefringence and layer spacing, demonstrating de Vries behavior for each, i.e., an unusually large increase in birefringence and an unusually small layer contraction. Both the induced changes in birefringence and layer spacing are shown to scale quadratically with the induced tilt angle.