Abstract

Understanding interfacial phenomena is important in processes like corrosion, catalysis, and electrochemical reactions. Specifically, in corrosion inhibition, the assembly of adsorbed surfactants at metal-water interfaces in well-packed, ordered layers is desired. We provide direct evidence of the role of alkyl tails of surfactants in the formation of ordered adsorbed layers at metal-water interfaces. We have employed surface-specific sum frequency generation (SFG) spectroscopy to probe the in situ adsorption and self-assembly of cationic surfactants, alkyldimethylbenzyl ammonium bromides of tail lengths n = 4 (C4) and 12 (C12), without any applied potential or stimulus, at the gold-water interface. Our SFG measurements show that C12 Quat adsorbs as an ordered monolayer, whereas C4 Quat adsorbs in a disordered monolayer. All-atom molecular dynamics (MD) simulations of these surfactants corroborate with SFG results. These findings provide new insights on how hydrophobic interactions between alkyl tails of surfactants affect their self-assembly at metal-water interfaces.

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