Molecular Orientations of Myristic Acid Derivatives with Different Perfluoroalkyl Chain Lengths at the Air/Water Interface Evaluated by Heterodyne-Detected Sum Frequency Generation Spectroscopy

Abstract

Surface-related properties of perfluoroalkyl compounds such as hydrophobicity and adhesion force can have a close relationship with the orientational order of the molecules at the surface. Myristic acid (MA) derivatives with perfluoroalkyl (Rf) groups have been known to form a well-ordered monolayer at the air/gold substrate interface. In this study, molecular orientations of the MA derivative monolayers at the air/water interface were investigated by heterodyne-detected vibrational sum frequency generation (HD-VSFG) spectroscopy. We estimated the molecular orientation of MA derivative monolayers with a marker band observed at around 1370 cm–1. The Rf chain length and the surface pressure dependence of the molecular orientation of four MA derivatives were examined. The marker bands were observed except for the derivative with the shortest Rf chain at the higher surface pressure, whereas the marker bands were observed only for the two derivatives with relatively longer Rf chain lengths at the lower surface pressure. The observation indicates that the longer the Rf chain is and the higher the surface pressure is, MA derivatives tend to adopt a standing orientation closer to perpendicular to the interface.