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

Rémi Dupuy; Jakob Filser; Clemens Richter; Robert Seidel; Florian Trinter; Tillmann Buttersack; Christophe Nicolas; John Bozek; Uwe Hergenhahn; Harald Oberhofer; Bernd Winter; Karsten Reuter; Hendrik Bluhm

doi:10.1039/D1CP05621B

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

Rémi Dupuy,

‡^a Jakob Filser,

‡^b Clemens Richter,^a Robert Seidel,

^c Florian Trinter,

^ad Tillmann Buttersack,

^a Christophe Nicolas,^e John Bozek,^e Uwe Hergenhahn,

^a Harald Oberhofer,

^bf Bernd Winter,

^a Karsten Reuter

*^a and Hendrik Bluhm*^a

Author affiliations

* Corresponding authors

^a Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany
E-mail: Reuter@fhi-berlin.mpg.de, Bluhm@fhi-berlin.mpg.de

^b Chair for Theoretical Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstr. 4, 85747 Garching, Germany

^c Helmholtz-Zentrum Berlin für Materialien und Energie, Albert-Einstein-Str. 15, 12489 Berlin, Germany

^d Institut für Kernphysik, Goethe-Universität Frankfurt am Main, Max-von-Laue-Straße 1, 60438 Frankfurt am Main, Germany

^e Synchrotron SOLEIL, L'Orme des Merisiers, Saint-Aubin - BP 48, Gif-sur-Yvette Cedex, France

^f Chair for Theoretical Physics VII and Bavarian Center for Battery Technology, University of Bayreuth, Universitätsstraße 30, 95447 Bayreuth, Germany

Abstract

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.

This article is part of the themed collection: 2022 PCCP HOT Articles

Physical Chemistry Chemical Physics

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

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