A TPD and RAIRS comparison of the low temperature surface behavior of benzene, toluene, and xylene on graphite

The first comparative study of the surface behavior of four small aromatic molecules, benzene, toluene, p-xylene, and o-xylene, adsorbed on graphite at temperatures ≤30 K, is presented. Intermolecular interactions are shown to be important in determining the growth of the molecules on the graphite surface at low (monolayer) exposures. Repulsive intermolecular interactions dominate the behavior of benzene and toluene. By contrast, stronger interactions with the graphite surface are observed for the xylene isomers, with islanding observed for o-xylene. Multilayer desorption temperatures and energies increase with the size of the molecule, ranging from 45.5 to 59.5 kJ mol^-1 for benzene and p-xylene, respectively. Reflection absorption infrared spectroscopy gives insight into the effects of thermal processing on the ordering of the molecules. Multilayer benzene, p-xylene, and o-xylene form crystalline structures following annealing of the ice. However, we do not observe an ordered structure for toluene in this study. The ordering of p-xylene shows a complex relationship dependent on both the annealing temperature and exposure.