Dynamics of Bound and Free Water in an Aqueous Micellar Solution : Analysis of the Lifetime and Vibrational Frequencies of Hydrogen Bonds at a Complex Interface

TL;DR

This study uses molecular dynamics simulations to analyze the lifetime and vibrational frequencies of hydrogen bonds in interfacial water molecules on a micellar surface, revealing differences between bound and free water dynamics.

Contribution

It provides detailed insights into the dynamics and vibrational properties of interfacial water molecules, validating the classification into bound and free types through simulation data.

Findings

Bound water molecules have longer hydrogen bond lifetimes.

Free water molecules behave similarly to bulk water in reorientation.

Interfacial water shows blue shifts in vibrational frequencies indicating increased rigidity.

Abstract

In order to understand the nature and dynamics of interfacial water molecules on the surface of complex systems, large scale molecular dynamics simulations of an aqueous micelle of cesium perfluorooctanoate surfactant molecules have been carried out. The lifetime and the intermolecular vibrational frequencies of the hydrogen bonds that the water molecules form with the polar headgroups of the surfactants, are calculated. Our earlier classification of the interfacial water molecules, based on structural and energetic considerations, into bound and free type is further validated by their dynamics. Lifetime correlation functions of the water-surfactant hydrogen bonds show the long lived nature of the bound water species. The water molecules that are singly hydrogen bonded to the surfactants have longer lifetime than those that form two such hydrogen bonds. The free water molecules that do not form any such hydrogen bonds behave similar to bulk water in their reorientational dynamics. A few water molecules that form two such hydrogen bonds are orientationally locked in for durations of the order of few hundreds of picoseconds. The intermolecular vibrational frequencies of these interfacial water molecules shows a significant blue shift in the librational band apart from a similar shift in the near neighbor bending modes, relative to water molecules in bulk. These blue shifts suggest an increase in rigidity in the structure around interfacial water molecules. This is in good agreement with recent incoherent, inelastic neutron scattering data on macromolecular solutions. The results of the present simulations should be relevant to the understanding of dynamics of water near any hydrophilic surface.