Liquid-solid interfaces density functional theory

The statistical mechanical approach, density functional theory, allows description of the solid-liquid interface based on knowledge of the liquid properties [60, 61], This approach has been applied to the solid-liquid interface for hard spheres where experimental data on colloidal suspensions and theory [62] both indicate 0.6 this... 

Molecular dynamics and density functional theory studies (see Section IX-2) of the Lennard-Jones 6-12 system determine the interfacial tension for the solid-liquid and solid-vapor interfaces [47-49]. The dimensionless interfacial tension ya /kT, where a is the Lennard-Jones molecular size, increases from about 0.83 for the solid-liquid interface to 2.38 for the solid-vapor at the triple point [49], reflecting the large energy associated with a solid-vapor interface. 

Chandra and his coworkers have developed analytical theories to predict and explain the interfacial solvation dynamics. For example, Chandra et al. [61] have developed a time-dependent density functional theory to predict polarization relaxation at the solid-liquid interface. They find that the interfacial molecules relax more slowly than does the bulk and that the rate of relaxation changes nonmonotonically with distance from the interface They attribute the changing relaxation rate to the presence of distinct solvent layers at the interface. Senapati and Chandra have applied theories of solvents at interfaces to a range of model systems [62-64]. 

For further reading, see Fundamentals of Inhomogeneous Fluids. D. Henderson, Ed. Marcel Dekker (1992). (Chapter 5 of this book, by R. Evans, describes the application of density functional theory) The Liquid-Solid Interface at High Resolution, Faraday Discuss. Roy. Soc. Chem. (London) (1992).)... 

Recently Haymet and Oxtoby and Klupsch ° independently develojjed related density functional theories of the liquid-solid interface. These are statistical mechanical theories that work with the grand canonical ensemble free energy Cl, which is a functional of the one-particle density p r),... 

Harrowell and Oxtoby have shown how the density functional theory for the solid-liquid interface outlined in Section III D can be generalized to study the nucleation of a crystal. If the critical nucleus is assumed spherical (a reasonable approximation for the alkali metals considered, given the near isotropy of the calculated surface free energy) then the inhomogeneous density of Eq. (3.13) can reasonably be generalized to... 

Over the last two decades the exploration of microscopic processes at interfaces has advanced at a rapid pace. With the active use of computer simulations and density functional theory the theory of liquid/vapor, liquid/liquid and vacuum/crystal interfaces has progressed from a simple phenomenological treatment to sophisticated ah initio calculations of their electronic, structural and dynamic properties [1], However, for the case of liquid/crystal interfaces progress has been achieved only in understanding the simplest density profiles, while the mechanism of formation of solid/liquid interfaces, emergence of interfacial excess stress and the anisotropy of interfacial free energy are not yet completely established [2],... 

Kierlik, E., Rosinberg, M.L., Fan, Y., and Monson, P. (1994). Prewetting at a liquid mixture-solid interface a comparison of Monte Carlo simulations with mean field density functional theory. J. Chem. Phys., 101, 10947-52. 

The series of 10 chapters that constitute Part 3 of the book deals mainly with the use of adsorption as a means of characterizing carbons. Thus, the first three chapters in this section complement each other in the use of gas-solid or liquid-solid adsorption to characterize the porous texture and/or the surface chemistry of carbons. Porous texture characterization based on gas adsorption is addressed in Chapter 11 in a very comprehensive manner and includes a description of a number of classical and advanced tools (e.g., density functional theory and Monte Carlo simulations) for the characterization of porosity in carbons. Chapter 12 illustrates the use of adsorption at the liquid-solid interface as a means to characterize both pore texture and surface chemistry. The authon propose these methods (calorimetry, adsorption from solution) to characterize carbons for use in such processes as liquid purification or liquid-solid heterogeneous catalysis, for example. Next, the surface chemical characterization of carbons is comprehensively treated in Chapter 13, which discusses topics such as hydrophilicity and functional groups in carbon as well as the amphoteric characteristics and electrokinetic phenomena on carbon surfaces. 

The first application of what would now be called density functional theory to the calculation of SFE was given by Ramakrishnan and Yussouff [115,116], although they did not use this terminology. A rederivation of their theory within the density functional context and a generalization to the theory of the solid-liquid interface was presented subsequently by Haymet and Oxtoby [117]. During the following decade this approach has been extensively developed and applied to a variety of problems. 

R. Jinnouchl and A. B. Anderson. Electronic structure calculations of liquid-solid Interfaces Combination of density functional theory and modified Poisson-Boltzmann theory. Phys. Rev. B, 77(245417), 2008. 

Abstract Recent advances in molecular modeling provide significant insight into electrolyte electrochemical and transport properties. The first part of the chapter discusses applications of quantum chemistry methods to determine electrolyte oxidative stability and oxidation-induced decomposition reactions. A link between the oxidation stability of model electrolyte clusters and the kinetics of oxidation reactions is established and compared with the results of linear sweep voltammetry measurements. The second part of the chapter focuses on applying molecular dynamics (MD) simulations and density functional theory to predict the structural and transport properties of liquid electrolytes and solid elecfiolyte interphase (SEI) model compounds the free energy profiles for Uthium desolvation from electrolytes and the behavior of electrolytes at charged electrodes and the electrolyte-SEl interface. 

Chen X, Sun L, Liu H, Hu Y, Jiang J A new lattice density functional theory for polymer adsorption at solid-liquid interface,/ Chem Phys 131(4) 044710, 2009. 

Density Functional Theories of Liquid-Solid Interfaces 1372... 

As a consequence of the spatial inhomogeneity of the liquid-solid interface, computational studies of these systems are, in general, far more complex than those on the corresponding bulk systems. This is reflected in both the large size of the calculations involved and in the greater programming effort required to perform such studies. Therefore, it is not surprising that the number of calculations on such systems is relatively small in comparison to the number of studies on bulk systems. The primary computational methods that have been used, to date, to study interfaces are computer simulation (both molecular dynamics and Monte Carlo methods) and classical density functional theory. 

DENSITY FUNCTIONAL THEORIES OF LIQUID-SOLID INTERFACES... 

As an example, it has been pointed out that the Hamaker and Lifshitz theories assume (exphcitly and implicitly, respectively) that intensive physical properties of the media involved such as density, and dielectric constant, remain unchanged throughout the phase—that is, right up to the interface between phases. We know, however, that at the atomic or molecular level solids and liquids (and gases under certain circumstances) exhibit short-range periodic fluctuations they are damped oscillating functions. Conceptually, if one visualizes a hquid in contact with a flat solid surface (Fig. 4.8a), one can see that the molecules (assumed to be approximately spherical, in this case) trapped between the surface and the bulk of the liquid will have less translational freedom relative to the bulk and therefore be more structured. That structure will (or may) result in changes in effective intensive properties near the surface. 

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