Laser-heating-induced displacement of surfactants on the water surface.

We report a combined vibrational sum-frequency generation (SFG) spectroscopy, Brewster angle microscopy (BAM), and ellipsometry study of different surfactants on water as a function of surfactant density. Vibrational SFG spectra of surfactants on the water surface in a Langmuir trough have been measured in both the surfactant CH and the water OH stretch regions. At low densities, the SFG signal generated at the surface in the presence of the surfactant is indistinguishable from the SFG signal generated at the clean water-air interface. When the surfactant density increases, i.e., upon compressing the monolayer, a very sudden increase in the SFG signal in both the CH and OH spectral regions is observed. For higher laser fluences, this stepwise increase occurs at increasingly higher surfactant densities. Since BAM shows that surfactant molecules are clearly present at these low densities, we conclude that at low surfactant density the laser beam displaces relatively high-density domains with surfactants in the liquid expanded phase out of the region of the laser focus. This is a consequence of the thermal gradient induced by local heating of the water phase with the monolayer on top due to repetitive laser excitation at 1 kHz. It can be circumvented by using a rotating trough. In this manner, the sampled surface area can be refreshed, allowing artifact-free vibrational SFG spectra to be measured down to the very lowest surfactant densities. In ellipsometry experiments, a similar step can be noticed, which, however, is of a different nature; i.e., it is not related to heating (the laser fluence is very low and the light nonresonant) but to a molecular transition. The occurrence of the step in ellipsometry as a function of area per molecule depends critically on the preparation of the monolayer. By giving the molecules time and space to relax during the preparation of the monolayer, this step could also be eliminated.