A MONTE CARLO STUDY OF CARBON MONOXIDE LAYERS ADSORBED ON IONIC SUBSTRATES: STRUCTURES AND PHASE TRANSITIONS

Abstract

We have studied the order–disorder phase transitions of carbon monoxide layers adsorbed on sodium chloride and lithium flouride substrates using the Metropolis Monte Carlo method. The simulations have been performed in the temperature range from 5 K to 60 K. At low temperature and monolayer coverage, both of these systems form ordered phases which disorder as the temperature is increased. The transition temperature (Tc) is between 30 K and 35 K for CO/NaCl, and from 40 K to 45 K for CO/LiF. Below Tc, both systems have an ordered p(2 × 1) type structure due to correlated azimuthal orientations. Above Tc, both systems undergo a phase transition to an azimuthally disordered p(1 × 1) structure, i.e. one with no preferred orientation in the surface plane. The heat capacity shows a characteristic divergence at the transition temperature. Coverages of less than a monolayer of the CO/NaCl system have also been studied. The CO molecules are found to aggregate and form islands with an ordered structure in the middle of the islands. These islands also undergo an order–disorder transition but at lower temperatures. Multilayer systems were found to destabilize the p(2 × 1) structure of the bottommost layer in favor of a p(1 × 1) structure with the upper layers adopting the bulk structure.