Effects of Charged Surfactants on Interfacial Water Structure and Macroscopic Properties of the Air‐Water Interface

Abstract Surfactants are used to control the macroscopic properties of the air‐water interface. However, the link between the surfactant molecular structure and the macroscopic properties remains unclear. Using sum‐frequency generation spectroscopy and molecular dynamics simulations, two ionic surfactants (dodecyl trimethylammonium bromide, DTAB, and sodium dodecyl sulphate, SDS) with the same carbon chain lengths and charge magnitude (but different signs) of head groups interact and reorient interfacial water molecules differently. DTAB forms a thicker but sparser interfacial layer than SDS. It is due to the deep penetration into the adsorption zone of Br − counterions compared to smaller Na + ones, and also due to the flip‐flop orientation of water molecules. SDS alters two distinctive interfacial water layers into a layer where H + points to the air, forming strong hydrogen bonding with the sulphate headgroup. In contrast, only weaker dipole‐dipole interactions with the DTAB headgroup are formed as they reorient water molecules with H + point down to the aqueous phase. Hence, with more molecules adsorbed at the interface, SDS builds up a higher interfacial pressure than DTAB, producing lower surface tension and higher foam stability at a similar bulk concentration. Our findings offer improved knowledge for understanding various processes in the industry and nature.