Transition Helmholtz free energy, entropy, and heat capacity of free-standing smectic films in water: A mean-field treatment

Using the extended McMillan's mean field approach with anisotropic forces a study of both the structural and thermodynamic properties of free-standing smectic film (FSSF) in water on heating to the isotropic temperature is carried out numerically. By solving the self-consistent nonlinear equations for the order parameters, we obtained that the smectic-A-isotropic (AI) transition occurs through the series of layer-thinning transitions causing the films to thin in the stepwise manner as the temperature is increased above the bulk smectic-A-isotropic temperature T_AI(bulk). With enhanced pair interactions in the bounding layers, the smectic-isotropic transition corresponds to smectic melting of the central layers. The effects of surface “enhanced” pair interactions in the bounding layers and of film thickness on the orientational and translational order parameters, the Helmholtz free energy and entropy, as well as the temperature dependence of the heat capacity of FSSFs, have also been investigated. Reasonable agreement between the theoretically predicted and the experimentally obtained – by means of optical microscopy and ellipsometry techniques – data of the temperature when the thin decylcyanobiphenyl smectic film immersing in water ruptures has been obtained