Structure and orientational ordering of nitrogen molecules physisorbed on graphite

Abstract

The structure and orientational ordering of nitrogen molecules physisorbed on graphite have been studied by low-energy diffraction (LEED). A two-sublattice in-plane herringbone structure with glide lines along two perpendicular directions is inferred from LEED patterns at T < 30 K from the monolayer where the molecular centers have the commensurate ( 3 × 3 ) 30° structure. The orientational order-disorder transition of this commensurate phase was examined by superlattice spot intensity and angular profile measurements for 20 < T < 38 K. A rapid drop in superlattice intensity is observed near 27 K. The persistence of some intensity to 38 K. is suggestive of residual short-range orientational ordering and perhaps finite size or heterogeneity effects. For increasing coverage at T = 15 K, there is first a transition to a previously unobserved uniaxial incommensurate phase and then a transition to an apparently triangular incommensurate phase. The orientational superlattice spots are clearly present in the uniaxial phase, but are much weaker in the triangular incommensurate phase. At 31 < T < 35 K, an apparently triangular incommensurate phase with no detectable orientational superlattice spots is observed. The lattice constant versus equilibrium vapor pressure curve has been determined in the latter case assuming a continuous transition. The lattice constants of the incommensurate phases are used to place limits on the extent of possible phase-coexistence regions between the commensurate, uniaxial incommensurate, and triangular incommensurate phases. The LEED patterns from the bilayer at T = 15 K indicate a double-period superlattice structure of the triangular incommensurate phase which does not have the glide line symmetries of the commensurate monolayer. Some effects of heterogeneity on these phase transitions are discussed. A phase diagram for 10 < T < 40 K is proposed.