Influence of surface commensurability on the structure and relaxation dynamics of a confined monatomic fluid

Molecular dynamics simulations are carried out for a single component, monatomic Lennard-Jones fluid confined between two mica surfaces to investigate the structure and relaxation dynamics of the confined fluid as a function of surface separation. Due to the underlying symmetry of the potassium ions on the mica surface, the contact layers prefer to adopt an incommensurate square or rhombic symmetry. The inner layers adopt a symmetry varying between rhombic, triangular, and square, depending on the density and surface separation. When the surface separation is an integral multiple of the particle diameter, distinct layering is observed, whereas jammed layers are formed at intermediate surface separations. This leads to the formation of both commensurate and incommensurate layering with varying intralayer symmetry. The self-intermediate scattering function exhibits a gamut of rich dynamics ranging from a distinct two-step relaxation indicative of glassy dynamics to slow relaxation processes where the correlations do not relax to zero over a microsecond for specific surface separations. An extended β relaxation is observed for both commensurate and incommensurate layering. Stretched exponential fits are used to obtain the relaxation times for the late α-relaxation regime of the self-intermediate scattering function. In some cases, we also observed dynamic and structural heterogeneities within individual layers. Although a single-component Lennard-Jones fluid does not exhibit a glass transition in the bulk, this study reveals that such a fluid can display, without supercooling, complex relaxation dynamics with signatures of a fluid approaching a glass transition upon confinement at constant temperature.