Structures of D2 layers on LiF(001).

Classical Monte Carlo (MC) simulations of D(2) molecules physisorbed on LiF(001) surfaces are reported and show a series of interesting commensurate structure forms, viz., p(2x2) -->p(8x2) -->p(4x2), with coverages Theta=0.5, 0.625, and 0.75, respectively, and are stable up to 8 K. These structures are consistent with recent helium atom scattering (HAS) results (the p(4x2) is not observed) in terms of coverage and stability, but disagree in terms of symmetry. The p(2x2) structure contains two D(2) molecules per unit cell, with each molecule lying parallel to the plane of the surface directly above every other cationic site. For the p(4x2) structure, there are two kinds of adsorption sites: a parallel site, as in the case of p(2x2), and a tilted site, where the D(2) molecules sit between cationic and anionic sites with the molecular axis directed toward the anionic site, with a tilt angle of theta approximately 63 degrees. Perturbation theory calculations show that the adsorbed D(2) molecules are azimuthally delocalized and hence the structures are indeed c-type. Our calculations also indicate that o-D(2) and helicoptering p-D(2) species prefer cationic sites, compared to cartwheeling p-D(2) species.