Resonant x-ray reflectivity measurements from the surface of liquid Bi22In78 find only a modest surface Bi enhancement, with 35 atomic % Bi in the first atomic layer. This is in contrast to the Gibbs adsorption in all liquid alloys studied to date, which show surface segregation of a complete monolayer of the low surface tension component. This suggests that surface adsorption in Bi-In is dominated by attractive interactions that increase the number of Bi-In neighbors at the surface. These are the first measurements in which resonant x-ray scattering has been used to quantify compositional changes induced at a liquid alloy surface.
X-ray reflectivity measurements of the binary liquid Ga-Bi alloy reveal a dramatically different surface structure above and below the monotectic temperature $T_{mono}=222^{circ}$ C. A Gibbs-adsorbed Bi monolayer resides at the surface at both regimes. However, a 30 {AA} thick, Bi-rich wetting film intrudes between the Bi monolayer and the Ga-rich bulk for $T > T_{mono}$. The internal structure of the wetting film is determined with {AA} resolution, showing a theoretically unexpected concentration gradient and a highly diffuse interface with the bulk phase.
We present x-ray reflectivity measurements from the free surface of a liquid gallium-bismuth alloy (Ga-Bi) in the temperature range close to the bulk monotectic temperature $T_{mono} = 222$C. Our measurements indicate a continuous formation of a thick wetting film at the free surface of the binary system driven by the first order transition in the bulk at the monotectic point. We show that the behavior observed is that of a complete wetting at a tetra point of solid-liquid-liquid-vapor coexistance.
We present x-ray reflectivity and diffuse scattering measurements from the liquid surface of pure potassium. They strongly suggest the existence of atomic layering at the free surface of a pure liquid metal with low surface tension. Prior to this study, layering was observed only for metals like Ga, In and Hg, the surface tensions of which are 5-7 fold higher than that of potassium, and hence closer to inducing an ideal hard wall boundary condition. The experimental result requires quantitative analysis of the contribution to the surface scattering from thermally excited capillary waves. Our measurements confirm the predicted form for the differential cross section for diffuse scattering, $dsigma /dOmega sim 1/q_{xy}^{2-eta}$ where $eta = k_BT q_z^2/2pi gamma $, over a range of $eta$ and $q_{xy}$ that is larger than any previous measurement. The partial measure of the surface structure factor that we obtained agrees with computer simulations and theoretical predictions.
We present a general computational scheme based on molecular dynamics (m.d.) simulation for calculating the chemical potential of adsorbed molecules in thermal equilibrium on the surface of a material. The scheme is based on the calculation of the mean force in m.d. simulations in which the height of a chosen molecule above the surface is constrained, and subsequent integration of the mean force to obtain the potential of mean force and hence the chemical potential. The scheme is valid at any coverage and temperature, so that in principle it allows the calculation of the chemical potential as a function of coverage and temperature. It avoids all statistical mechanical approximations, except for the use of classical statistical mechanics for the nuclei, and assumes nothing in advance about the adsorption sites. From the chemical potential, the absolute desorption rate of the molecules can be computed, provided the equilibration rate on the surface is faster than the desorption rate. We apply the theory by {em ab initio} m.d. simulation to the case of H$_2$O on MgO (001) in the low-coverage limit, using the Perdew-Burke-Ernzerhof (PBE) form of exchange-correlation. The calculations yield an {em ab initio} value of the Polanyi-Wigner frequency prefactor, which is more than two orders of magnitude greater than the value of $10^{13}$ s$^{-1}$ often assumed in the past. Provisional comparison with experiment suggests that the PBE adsorption energy may be too low, but the extension of the calculations to higher coverages is needed before firm conclusions can be drawn. The possibility of including quantum nuclear effects by using path-integral simulations is noted.
We construct a mean-field formulation of the thermodynamics of ion solvation in immiscible polar binary mixtures. Assuming an equilibrium planar interface separating two semi-infinite regions of different constant dielectric medium, we study the electrostatic phenomenon of differential adsorption of ions at the interface. Using general thermodynamic considerations, we construct the mean-field $Omega$-potential and demonstrate the spontaneous formation of an electric double-layer around the interface necessarily follow. In our framework, we can also relate both the bulk ion densities in the two phases and the distribution potential across the interface to the fundamental Born free energy of ion polarization. We further illustrate this selective ion adsorption phenomenon in respective examples of fully permeable membranes that are neutral, negative, or positive in charge polarity.