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

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

Designing all-graphene nanojunctions by covalent functionalization

We investigated theoretically the effect of covalent edge functionalization, with organic functional groups, on the electronic properties of graphene nanostructures and nano-junctions. Our analysis shows that functionalization can be designed to tune electron affinities and ionization potentials of graphene flakes, and to control the energy alignment of frontier orbitals in nanometer-wide graphene junctions. The stability of the proposed mechanism is discussed with respect to the functional groups, their number as well as the width of graphene nanostructures. The results of our work indicate that different level alignments can be obtained and engineered in order to realize stable all-graphene nanodevices

A critical assessment of methods for the intrinsic analysis of liquid interfaces. 1. surface site distributions

Substantial progress in our understanding of interfacial structure and dynamics has stemmed from the recent development of algorithms that allow for an intrinsic analysis of fluid interfaces. These work by identifying the instantaneous location of the interface, at the atomic level, for each molecular configuration and then computing properties relative to this location. Such a procedure eliminates the broadening of the interface caused by capillary waves and reveals the underlying features of the system. However, a precise definition of which molecules actually belong to the interfacial layer is difficult to achieve in practice. Furthermore, it is not known if the different intrinsic analysis methods are consistent with each other and yield similar results for the interfacial properties. In this paper, we carry out a systematic and detailed comparison of the available methods for intrinsic analysis of fluid interfaces, based on a molecular dynamics simulation of the interface between liquid water and carbon tetrachloride. We critically assess the advantages and shortcomings of each method, based on reliability, robustness, and speed of computation, and establish consistent criteria for determining which molecules belong to the surface layer. We believe this will significantly contribute to make intrinsic analysis methods widely and routinely applicable to interfacial systems

Solvation free energy profile of the SCN- ion across the water-1,2-dichloroethane liquid/liquid interface. A computer simulation study

The solvation free energy profile of a single SCN- ion is calculated across the water-1,2-dichloroethane liquid/liquid interface at 298 K by the constraint force method. The obtained results show that the free energy cost of transferring the ion from the aqueous to the organic phase is about 70 kJ/mol, The free energy profile shows a small but clear well at the aqueous side of the interface, in the subsurface region of the water phase, indicating the ability of the SCN- ion to be adsorbed in the close vicinity of the interface. Upon entrance of the SCN- ion to the organic phase a coextraction of the water molecules of its first hydration shell occurs. Accordingly, when it is located at the boundary of the two phases the SCN- ion prefers orientations in which its bulky S atom is located at the aqueous side, and the small N atom, together with its first hydration shell, at the organic side of the interface

Properties of the liquid–vapor interface of acetone–methanol mixtures, as seen from computer simulation and ITIM surface analysis

Molecular dynamics simulations of the liquid–vapor interface of acetone–methanol mixtures of different compositions, including the two neat systems, have been performed on the canonical (N,V,T) ensemble at 293 K. The intrinsic liquid surface has been determined in terms of the Identification of the Truly Interfacial Molecules (ITIM) method. The results have revealed that the proximity of the interface influences the properties of only the first molecular layer of the liquid phase, while the second layer already turns out to be bulk-like in every respect. The two molecules are distributed uniformly along the macroscopic surface normal axis, as no strong preference for surface adsorption is shown by any of them. However, similarly to the bulk liquid phase, both molecules exhibit a marked tendency for self-association within the surface layer. Surface orientations are found to be composition independent; all the preferred orientations of both molecules correspond to the same alignment of the molecular dipole vector, which is nearly parallel to the macroscopic surface plane, declining only 10–20° from it towards the vapor phase. The surface properties are thus primarily governed by dipolar interactions, whereas hydrogen bonding within the surface layer, which decreases steadily with an increase in the acetone mole fraction, plays only a minor role in this respect

Molecular level properties of the free water surface and different organic liquid/water interfaces, as seen from ITIM analysis of computer simulation results

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