Structure of octadecanol monolayers:: An x-ray diffraction study

Octadecanol monolayers at the air/water interface are studied by grazing incidence x-ray diffraction. At low lateral pressures one observes the diffraction patterns inherent to the next-nearest neighbor tilt of the molecules. The unit cells are found to be distorted at both low (6 degrees C) and high (33 degrees C) temperatures due to tilt of the molecules and ordering of their backbones. Unexpectedly, at an intermediate temperature of 22 degrees C, the unit cell remains hexagonal in the water plane, despite the tilt of the molecules. This behavior is treated in terms of hydrogen bonding with the water molecules and does not imply the existence of a separate phase. Our diffraction study also does not show any indication of a phase transition S*-L-2* corresponding to the singularities in the isotherms within the tilted phase. The tilting phase transitions from untilted phases S and LSII seem to be continuous, since the transition pressures obtained by extrapolation of the tilt angle to zero tilt coincide with the ones determined by Brewster angle microscopy. (C) 1998 American Institute of Physics.