Abstract
The development of smectic-A ordering at the interface between isotropic liquid and vapor is studied using a density-functional theory, based on a mean-field approximation for the effect of attractive pair interactions and weighted-density treatment of repulsive-core contributions. In contrast to earlier microscopic theories of this phenomenon, the bulk liquid and vapor phases are in complete coexistence with each other, and no arbitrary ``surface fields'' independent of molecular pair interactions are invoked. The wetting behavior of the interface is studied as a function of the molecular-core anisotropy, which controls the relative stability of bulk nematic and smectic-A phases, under conditions where the attractive pair interactions favor complete wetting by the nematic phase. There is a change to incomplete wetting by the smectic-A phase when the latter preempts the nematic, in a process analogous to a triple-point wetting transition. This is consistent with experimental results, but the growth of smectic layers at the interface is always found to be continuous, with no evidence of the first-order layering transitions observed in experiment.
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