A Synchrotron X-ray Study of a Solid-Solid Phase Transition in a Two-Dimensional Crystal
SHARON GRAYER WOLF 1,
EHUD M. LANDAU 1,
MEIR LAHAV 1,
LESLIE LEISEROWITZ 1,
MOSHE DEUTSCH 2,
KRISTIAN KJAER 3, and
JENS ALS-NIELSEN 3
1 Structural Chemistry Department, Weizmann Institute of Science, Rehovot 76100, Israel.
2 Physics Department, Bar-Ilan University, Ramat Gan 52100, Israel.
3 Physics Department, Risø National Laboratory, DK4000 Roskilde, Denmark.
A measurement and interpretation on a molecular level of a phase transition in an ordered Langmuir monolayer is reported. The diagram of surface pressure (
) versus molecular area of a monolayer of chiral (S)-[CF3-(CF2)9-(CH2)2-OCO-CH2-CH (NH3+)CO2-] over water shows a change in slope at about
s= 25 millinewtons per meter. Grazing-incidence x-ray diffraction and specular reflectivity measurements indicate a solid-solid phase transition at
s. The diffraction pattren at low pressures reveals two diffraction peaks of equal intensities, with lattice spacings d of 5.11 and 5.00 angstroms; these coalesce for

s. Structural models that fit the diffraction data show that at
>
s the molecules pack in a two-dimensional crystal with the molecules aligned vertically. At
<
s there is a molecular tilt of 16 ° ± 7 °. Independent x-ray reflectivity data yield a tilt of 26 ° ± 7°. Concomitant with the tilt, the diffraction data indicate a transition from a hexagonal to a distorted-hexagonal lattice. The hexagonal arrangement is favored because the -(CF2)9CF3 moiety adopts a helical conformation. Compression to 70 millinewtons per meter yields a unit cell with increased crystallinity and a coherence length exceeding 1000 angstroms.
Submitted on June 1, 1988
Accepted on September 7, 1988