Photoelectron angular distributions as sensitive probes of surfactant layer structure at the liquid-vapor interface

R Dupuy and J Filser and C Richter and R Seidel and F Trinter and T Buttersack and C Nicolas and J Bozek and U Hergenhahn and H Oberhofer and B Winter and K Reuter and H Bluhm, PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 24, 4796-4808 (2022).

DOI: 10.1039/d1cp05621b

The characterization of liquid-vapor interfaces at the molecular level is an important underpinning for a basic understanding of fundamental heterogeneous processes in many areas, such as atmospheric science. Here we use X-ray photoelectron spectroscopy to study the adsorption of a model surfactant, octanoic acid, at the water-gas interface. In particular, we examine the information contained in photoelectron angular distributions and show that information about the relative depth of molecules and functional groups within molecules can be obtained from these measurements. Focusing on the relative location of carboxylate (COO-) and carboxylic acid (COOH) groups at different solution pH, the former is found to be immersed deeper into the liquid-vapor interface, which is confirmed by classical molecular dynamics simulations. These results help establish photoelectron angular distributions as a sensitive tool for the characterization of molecules at the liquid-vapor interface.

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