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Title: Structure And Dynamics Of Interfacial And Confined Water
Authors: Malani, Ateeque Ahmad Abdul Gaffar
Advisors: Ayappa, K G
Keywords: Interfacial Water
Water - Interfacial Properties
Water Structure
Water - Thermodynamics
Water - Transport Properties
Confined Water
Water Adsorption
Submitted Date: Mar-2009
Series/Report no.: G23069
Abstract: Understanding the structure and dynamics of molecularly thin films or the state of water confined to nanoscale dimensions is an active field of research and has wide applications in areas ranging from biology to geology. The issues concern fundamental aspects related to the manner in which a substrate influences the organization of water, origin of forces present when water is confined to nanoscale dimensions, and the influence on the structure and dynamics of water adjacent to a surface. The focus of this thesis lies in examining the thermodynamics and transport properties of interfacial and confined water. As a prelude to studying the structure of water confined between two mica surfaces, we first investigated the structuring of water adjacent to a single mica surface using grand canonical Monte Carlo (GCMC) simulations. The adsorption isotherm reveals three distinct stages as the relative vapor pressure in increased. The derived film thickness, isotherm shape, and heats of adsorption are in excellent agreement with recent experimental data. Our study does not support the 2D ice hypothesis and indicates that beyond the first adsorbed layer water is liquid-like. The characteristics of water confined to nanometer dimensions between two hydrophilic surfaces are investigated to assess the influence of chemical functionality of the hydrophilic surface on the structure of confined water. Our study shows that hydration of potassium ions on the mica surface has a strong influence on the water structure and solvation force response of confined water. In contrast to the disrupted hydrogen bond network observed for water confined between mica surfaces, water between silica surfaces is able to retain its hydrogen bond network displaying bulk-like structural features down to surface separations as small as 0.45 nm. An oscillatory solvation force response is observed only for water confined between silica surfaces. We evaluate and contrast the water density, dipole moment distributions, pair correlation functions and the solvation forces as a function of the surface separation. Recent experimental studies have shown that even for subnanometer confinement, the shear viscosity of water between mica surfaces is only three times larger than the free water viscosity. The dynamics of confined water between mica surfaces is evaluated using molecular dynamics simulations. Our analysis shows that the residence time for water in the contact layer is about two orders of magnitude larger than water in the central bulk-like regions between the surfaces. The K+ ions have a strong influence on the dynamics of confined water, leading to a decoupling in the translation and orientational motions. Our analysis also shows the presence of orientational jump dynamics in the contact layer near the mica surface. We also investigate the influence of confinement on the hydration characteristics of NaCl solutions both as a function of the salt concentration and the surface separation, H between graphite surfaces. A hydration limit is defined as the concentration at which a rapid drop in the hydration number is observed with increasing salt concentration. Despite a high degree of confinement, ions are able to form a quasi two-dimensional hydration shell between the two surfaces. The hydration number, reduces to about 4.15 at a pore width of H =8 A, when compared with the bulk hydration number of 6.25. In many practical situations, surfaces that are separated by an intervening fluid can be dissimilar giving rise to the so called Janus interface. In order to probe the fluid structure in such systems, we studied non-polar fluids confined between two asymmetric surfaces. By varying the degree of asymmetry between the two surfaces a wide variety of adsorption situations are examined using GCMC simulations and a mean field lattice model. The degree of asymmetry is found to influence the presence of frozen phases and can also support co-existing liquid and solid phases.
URI: http://hdl.handle.net/2005/1100
Appears in Collections:Chemical Engineering (chemeng)

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