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Using molecular dynamics simulations, we study freezing of Lennard-Jones particles at commensurate substrate with triangular pattern. Throughout the box particles freeze onto the substrate and form close-packed layers. For the moderately attractive substrates, an intermediate hexatic phase between liquid and crystal is detected in the first two layers where the hexatic-solid freezing process is continuous while, counterintuitively, the liquid-hexatic process is of first order. Moreover, we observe that liquid-hexatic and hexatic-solid transitions shift towards higher temperatures with the attraction strength increasing. By contrast, the liquid-hexatic transition shifts faster than the hexatic-solid process, significantly widening the temperature range of the hexatic phase. When this phenomenon appears, freezing in the bulk always proceeds through a first-order transition at the same temperature. In addition, changes in the average structural order (three-dimensional) of the layers indicate that freezing processes in layers near substrates seem to cost the structural order of the bulk particles in their vicinity, and an intermediate prestructural cloud of medium-ordered particles is always observed before the layering freezing. [ABSTRACT FROM AUTHOR]

Molecular dynamics simulations of the Lennard-Jones model are used to study phase transitions at a smooth surface. Our motivation is the observation that the existence of an attractive wall facilitates crystallization. To investigate how this wall influences phase transitions, the strength of wall-particle interaction is varied in our studies. We find that the phase behavior depends on the strength parameter α, i.e., the ratio between wall-particle and the particle-particle attraction strength. Three critical values of the ratio, namely, αp, αw, and αc, are used to define the qualitative nature of the phase behaviors at a smooth surface. Some interesting phenomena due to the increase of α are observed. First, a set of close-packed planes, i.e., {111} planes in fcc structures or {0001} planes in hcp structures, are "rotated" from intersecting to parallel to the wall when α = αp; second, the layering phase transition close to the wall antecedes that of the bulk when α = αw. Finally, the first-order phase transition in the first two layers is supplanted by a continuous phase transition when α = αc, which to some extent can be treated as a quasi-two-dimensional process. We find that bulk freezing always discontinuously occurs through a first-order phase transition, and seems to be isolated from the freezing process occurring close to the attractive surfaces. Moreover, during the heating process, we observe minimal dependence at a strongly attractive surface. [ABSTRACT FROM AUTHOR]