Surface electroclinic effect near the first-order smectic-A*-smectic-C* transition

We analyze the surface electroclinic effect (SECE) in a material that exhibits a first-order bulk smectic-A* (Sm-A*)-smectic-C* (Sm-C*) transition. The effect of a continuously varying degree of enantiomeric excess on the SECE is also investigated. We show that due to the first-order nature of the bulk Sm-A*-Sm-C* transition, the SECE can be unusually strong and that as enantiomeric excess is varied, a jump in surface induced tilt is expected. A theoretical state map, in enantiomeric excess-temperature space, features a critical point which terminates a line of first-order discontinuities in the surface induced tilt. This critical point is analogous to that found for the phase diagram (in electric field-temperature space) for the bulk electroclinic effect. Analysis of the decay of the surface induced tilt, as one moves from surface into bulk, shows that for sufficiently high-surface tilt the decay will exhibit a well-defined spatial kink within which it becomes especially rapid. We also propose that the SECE is additionally enhanced by the de Vries nature (i.e., small layer shrinkage at the bulk Sm-A*-Sm-C* transition) of the material. As such, the SECE provides a new means to characterize the de Vries nature of a material. We discuss the implications for using these materials in device applications and propose ways to investigate the predicted features experimentally.