Raman studies in SmCFI* phases

The study of the Raman intensity of the 'breathing' mode of the benzene rings as a function of the temperature in smectic phases revealed strong anomalies of the intensities I_ZZ and I_YY in SmC_FI2* and SmC_FI1* phases, as well as an important shift of the principal optical direction with respect to other smectic phases. The analysis of these results provided evidence for significant structural changes at the SmC*-SmC_FI* and SmC_FI*-SmC_A* phase transitions, because the molecules can no longer be treated as cylindrical rods. No anomalies in the tilt angle were found. Experimental results suggest a relationship between the deviation of the optical axis and the particular structure of the SmC_FI* phases. The deviation of I_ZZ maxima as a function of the rotation angle Ψ and the behaviour evident under an electric field in SmC_FI* and SmC_A* phases clearly excludes the coexistence of SmC_A* and SmC* local domains in SmC_FI* phases.