Local structure of liquid/vapour interfaces approaching the critical point

Investigating the structure of fluid interfaces at high temperatures is a particularly delicate task that requires effective ways of discriminating liquid from vapour and identifying the location of the liquid phase boundary, thereby allowing to distinguish intrinsic from capillary fluctuations. Several numerical approaches require introducing a coarse-graining length scale, often heuristically chosen to be the molecular size, to determine the location of the liquid phase boundary. Here, we propose an alternative rationale for choosing this coarse-graining length scale; we require the average position of the local liquid phase dividing surface to match its flat, macroscopic counterpart. We show that this approach provides additional insight into the structure of the liquid/vapour interface, suggesting the presence of another length scale beyond the bulk correlation one that plays an important role in determining the interface structure

Instantaneous Normal Mode analysis of liquid HF

We present an Instantaneous Normal Modes analysis of liquid HF aimed to clarify the origin of peculiar dynamical properties which are supposed to stem from the arrangement of molecules in linear hydrogen-bonded network. The present study shows that this approach is an unique tool for the understanding of the spectral features revealed in the analysis of both single molecule and collective quantities. For the system under investigation we demonstrate the relevance of hydrogen-bonding ``stretching'' and fast librational motion in the interpretation of these features.Comment: REVTeX, 7 pages, 5 eps figures included. Minor changes in the text and in a figure. Accepted for publication in Phys. Rev. Let

Two-dimensional percolation at the free water surface and its relation with the surface tension anomaly of water

The percolation temperature of the lateral hydrogen bonding network of the molecules at the free water surface is determined by means of molecular dynamics computer simulation and identification of the truly interfacial molecules analysis for six different water models, including three, four, and five site ones. The results reveal that the lateral percolation temperature coincides with the point where the temperature derivative of the surface tension has a minimum. Hence, the anomalous temperature dependence of the water surface tension is explained by this percolation transition. It is also found that the hydrogen bonding structure of the water surface is largely model-independent at the percolation threshold; the molecules have, on average, 1.90 +/- 0.07 hydrogen bonded surface neighbors. The distribution of the molecules according to the number of their hydrogen bonded neighbors at the percolation threshold also agrees very well for all the water models considered. Hydrogen bonding at the water surface can be well described in terms of the random bond percolation model, namely, by the assumptions that (i) every surface water molecule can form up to 3 hydrogen bonds with its lateral neighbors and (ii) the formation of these hydrogen bonds occurs independently from each other. (C) 2014 AIP Publishing LLC

Microscopic dynamics and relaxation processes in liquid Hydrogen Fluoride

Inelastic x-ray scattering and Brillouin light scattering measurements of the dynamic structure factor of liquid hydrogen fluoride have been performed in the temperature range$T=214\div 283 K$. The data, analysed using a viscoelastic model with a two timescale memory function, show a positive dispersion of the sound velocity $c(Q)$ between the low frequency value $c_0(Q)$ and the high frequency value $c_{\infty \alpha}(Q)$. This finding confirms the existence of a structural ($\alpha$) relaxation directly related to the dynamical organization of the hydrogen bonds network of the system. The activation energy $E_a$ of the process has been extracted by the analysis of the temperature behavior of the relaxation time $\tau_\alpha(T)$ that follows an Arrhenius law. The obtained value for $E_a$, when compared with that observed in another hydrogen bond liquid as water, suggests that the main parameter governing the $\alpha$-relaxation process is the number of the hydrogen bonds per molecule.Comment: 9 pages and 12 figure

Towards an effective potential for the monomer, dimer, hexamer, solid and liquid forms of hydrogen fluoride

We present an attempt to build up a new two-body effective potential for hydrogen fluoride, fitted to theoretical and experimental data relevant not only to the gas and liquid phases, but also to the crystal. The model is simple enough to be used in Molecular Dynamics and Monte Carlo simulations. The potential consists of: a) an intra-molecular contribution, allowing for variations of the molecular length, plus b) an inter-molecular part, with three charged sites on each monomer and a Buckingham "exp-6" interaction between fluorines. The model is able to reproduce a significant number of observables on the monomer, dimer, hexamer, solid and liquid forms of HF. The shortcomings of the model are pointed out and possible improvements are finally discussed.Comment: LaTeX, 24 pages, 2 figures. For related papers see also http://www.chim.unifi.it:8080/~valle

Nonzero Ideal Gas Contribution to the Surface Tension of Water

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Properties of the Liquid-Vapor Interface of Acetone-Water Mixtures. A Computer Simulation and ITIM Analysis Study

Molecular dynamics simulations of the liquid-vapor interface of acetone-water mixtures of different compositions, covering the entire composition range have been performed on the canonical (N, V, T) ensemble at 298 K, using a model combination that excellently describes the mixing properties of these compounds. The properties of the intrinsic liquid surfaces have been analyzed in terms of the Identification of the Truly Interfacial Molecules (ITIM) method. Thus, the composition, width, roughness, and separation of the subsurface molecular layers, as well as self-association, orientation, and dynamics of exchange with the bulk phase of the surface molecules have been analyzed in detail. Our results show that acetone molecules are strongly adsorbed at the liquid surface, and this adsorption extends to several molecular layers. Like molecules in the surface layer are found to form relatively large lateral self-associates. The effect of the vicinity of the vapor phase on a number of properties of the liquid phase vanishes beyond the first molecular layer, with the second subsurface layer already part of the bulk liquid phase in these respects. The orientational preferences of the surface molecules are governed primarily by the dipole-dipole interaction of the neighboring acetone molecules, and hydrogen bonding interaction of the neighboring acetone-water pairs. (Figure Presented). © 2015 American Chemical Society

Floating Patches of HCN at the Surface of Their Aqueous Solutions - Can They Make "HCN World" Plausible?

The liquid/vapor interface of the aqueous solutions of HCN of different concentrations has been investigated using molecular dynamics simulation and intrinsic surface analysis. Although HCN is fully miscible with water, strong interfacial adsorption of HCN is observed at the surface of its aqueous solutions, and, at the liquid surface, the HCN molecules tend to be located even at the outer edge of the surface layer. It turns out that in dilute systems the HCN concentration can be about an order of magnitude larger in the surface layer than in the bulk liquid phase. Furthermore, HCN molecules show a strong lateral self-association behavior at the liquid surface, forming thus floating HCN patches at the surface of their aqueous solutions. Moreover, HCN molecules are staying, on average, an order of magnitude longer at the liquid surface than water molecules, and this behavior is more pronounced at smaller HCN concentrations. Because of this enhanced dynamical stability, the floating HCN patches can provide excellent spots for polymerization of HCN, which can be the key step in the prebiotic synthesis of partially water-soluble adenine. All of these findings make the hypothesis of "HCN world" more plausible