X-ray reflectivity (XR) and diffraction at grazing angles of incidence (GID
) were conducted to determine the structure of synthetic D-erythro C18-cera
mide films at the air-water interface at various surface pressures (pi). An
alysis of the GID reveals that the monomolecular film, at the crystalline p
hase (pi > 0 mN/m), is predominantly hexagonal. In this crystalline phase,
the analysis of the reflectivity yields an electron density profile that co
nsists of three distinct homogeneous slabs, one associated with the headgro
up region and the other two with the hydrocarbon chains. At large molecular
areas (pi approximate to 0), isolated crystalline domains coexist with two
-dimensional gas phase. Within the crystalline domains, we find an orthorho
mbic arrangement of the chains that coexists with the hexagonal symmetry. I
t is argued that the two-dimensional orthorhombic crystals are induced by h
ydrogen bonding between headgroups even at very low surface pressures. Alth
ough their structure is incommensurate with the simple hexagonal arrangemen
t, they act as nucleation centers for the conventional hexagonal phase whic
h dominates at high pi.