Interfacial Inversion, Interference, and IR Absorption in Vibrational Sum Frequency Scattering Experiments.

ABSTRACT

Molecular interfacial structure greatly determines the properties of nano- and microscale systems. Vibrational sum frequency scattering (SFS) spectroscopy is a unique interface-selective tool to measure the interfacial vibrational spectrum of sub-micron to micron-scale objects dispersed in liquid and solid media. The interfacial structure is extracted from the interfacial susceptibility, a physical property derived from the intensity. Here, we describe the effect of infrared absorption that occurs in a bulk medium that is spectroscopically complex and use the results to investigate the effects of interfacial inversion, interfacial interference, and interfacial interference combined with absorption. We use the same three chemicals to do so, hexadecane oil, water, and a neutral Span80 surfactant. For all cases, the effective surface susceptibility can be retrieved from the intensity. We further find that inverting the phases results in different interfacial structures, even though they are composed of the same three chemicals, and explain this in terms of the different interactions that are necessary to stabilize the drops steric stabilization for water drops in oil vs. charge stabilization for oil drops in water. Interfacial interference can be used to estimate the surface density of different compounds.