Cation-induced monolayer collapse at lower surface pressure follows specific headgroup percolation.

Abstract

A Langmuir monolayer can be considered as a two-dimensional (2D) sheet at higher surface pressure which structurally deform with mechanical compression depending upon the elastic nature of the monolayer. The deformed structures formed after a certain elastic limit are called collapsed structures. To explore monolayer collapses at lower surface pressure and to see the effect of ions on such monolayer collapses, out-of-plane structures and in-plane morphologies of stearic acid Langmuir monolayers have been studied both at lower (≈6.8) and higher (≈9.5) subphase pH in the presence of Mg^{2+},Ca^{2+},Zn^{2+},Cd^{2+}, and Ba^{2+} ions. At lower subphase pH and in the presence of all cations, the stearic acid monolayer remains as a monolayer before collapse, which generally takes place at higher surface pressure (π_{c}>50mN/m). However, at higher subphase pH, structural changes of stearic acid monolayers occur at relatively lower surface pressure depending upon the specific dissolved ions. Among the same group elements of Mg^{2+},Ca^{2+}, and Ba^{2+}, only for Ba^{2+} ions does monolayer to multilayer transition take place from a much lower surface pressure of the monolayer, remaining, however, as a monolayer for Mg^{2+} and Ca^{2+} ions. For another same group elements of Zn^{2+} and Cd^{2+} ions, a less covered bilayer structure forms on top of the monolayer structure at lower surface pressure, which is evidenced from both x-ray reflectometry and atomic force microscopy. Fourier transform infrared spectroscopy confirms the presence of two coexisting conformations formed by the two different metal-headgroup coordinations and the monolayer to trilayer or multilayer transformation takes place when the coverage ratio of the two molecular conformations changes from the critical value (p_{c}) of ≈0.66. Such ion-specific monolayer collapses are correlated with the 2D lattice percolation model.