Adsorbed species on single crystal surfaces are frequently found to exhibit long-range ordering; that is to say that the adsorbed species form a well-defined overlayer structure. Each particular structure may only exist over a limited coverage range of the adsorbate, and in some adsorbate/substrate systems a whole progression of adsorbate structure are formed as the surface coverage is gradually increased.
The periodicity of the overlayer (which often is larger than that of the substrate unit cell) can be determined by low-energy electron diffraction (LEED), because there will be additional diffraction beams associated with the overlayer.