Various molecules are known to form self-assembled monolayers (SAMs) on the surface of liquids. We present a simple method of investigating the kinetics of such SAM formation on sessile drops of various liquids such as mercury, water and fluorocarbon. To measure the surface tension of the drops we used an optical tensiometer that calculates the surface tension from the axisymmetric drop shape and the Young-Laplace relation. In addition, we estimated the SAM surface coverage fraction from the surface tension measured by other techniques. With this methodology we were able to optically detect concentrations as low as tenths of ppb increments of SAM molecules in solution and to compare the kinetics of SAM formation measured as a function of molecule concentration or chain length. The analysis is performed in detail for the case of alkanethiols on mercury and then shown to be more general by investigating the case of SAM formation of stearic acid on a water droplet in hexadecane and of perfluorooctanol on a Fluorinert FC-40 droplet in ethanol.

Self-assembled organic films on liquid metals feature a very rich phase behavior, which qualitatively differs from the one on crystalline metals. In contrast to conventional crystalline supports, self-assembled alkylthiol monolayers on liquid metals possess a considerably higher degree of molecular order, thus enabling much more robust metal-molecule-semiconductor couplings for organic electronics applications. Yet, compared to crystalline substrates, the self-assembly of organic surfactants on liquid metals has been studied to a much lesser extent. In this Letter we report the first of its kind molecular simulation investigation of alkyl-based surfactants on a liquid mercury surface. The focus of our investigation is the surfactant conformations as a function of surface coverage and surfactant type. First, we consider normal alkanes because these systems set the basis for simulations of all other organic surfactants on liquid mercury. Subsequently, we proceed with the discussion of alkylthiols that are the most frequently used surfactants in the surface science of hybrid organometallic interfaces. Our results indicate a layering transition of normal alkanes as well as alkylthiols from an essentially bare substrate to a completely filled monolayer of laying molecules. As the surface coverage increases further, we observe a partial wetting of the laying monolayer by the bulk phase of alkanes. In the case of alkylthiols, we clearly see the coexistence of molecules in laying-down and standing-up conformations, in which the sulfur headgroups of the thiols are chemically bound to mercury. In the standing-up phase, the headgroups form an oblique lattice. For the first time we were able to explicitly characterize the molecular-scale structure and transitions between phases of alkyl-based surfactants and to demonstrate how the presence of a thiol headgroup qualitatively changes the phase equilibrium and structure in these systems. The observed phenomena are consistent with available direct and indirect experimental evidence.

Motivated by an experimental interest we investigate by the means of atomistic Molecular Dynamics simulation the ability of density-independent, empiric density-dependent, and recently proposed embedded-atom force fields for liquid mercury to predict the surface tension of the free surface of liquid mercury at the temperature of 293 K. The effect of the density dependence of the studied models on the liquid-vapor coexistence and surface tension is discussed in detail. In view of computational efficiency of the density-independent model we optimize its functional form to obtain higher surface tension values in order to improve agreement with experiment. The results are also corroborated by Monte Carlo simulations and semi-analytic estimations of the liquid-vapor coexistence density. *

We report computer simulation of the self-assembly of alkylthiols on the surface of liquid mercury. Here we focus mainly on the alkylthiol behavior on mercury as a function of the surfactant surface coverage, which we study by means of large-scale molecular dynamics simulations of the equilibrium structure at room temperature. The majority of the presented results are obtained for octa- and dodecanethiol surfactants. This topic is particularly interesting because the properties of the alkylthiol self-assembled monolayers on liquid mercury are relevant for practical applications (e.g., in organic electronics) and can be controlled by mechanically manipulating the monolayer, i.e., by changing its structure. Our computer simulation results shed additional light on the alkylthiol self-assembly on liquid mercury by revealing the coexistence of a dense agglomerated laying-down alkylthiols with a very dilute 2D vapor on mercury surface rather than a single vapor phase in the low surface coverage regime. In the regimes of the high surface coverage we observe the coexistence of the laying-down liquid phase and crystalline phases with alkylthiols standing tilted at a sharp angle to the surface normal, which agrees with the phase behavior previously seen in X-ray and tensiometry experiments. We also discuss the influence of finite-size effects, which one inevitably encounters in molecular simulations. Our findings agree well with the general predictions of the condensation/evaporation theory for finite systems. The temperature dependence of the stability of the crystalline alkylthiol phases and details of the surfactant chemical binding to the surface are discussed. The equilibrium structure of the crystalline phase is investigated in detail for the alkylthiols of various tail lengths.

2. К л у ш а н ц е в Б.В. Щековые дробилки. Сб. Оборудование для промышленности строительных материалов «Сер. П».-М.: ЦНИИТЭ строймаш, 1972.-44 с. 3. К о р ш у н о в Л. Г. // ФММ. 1992. № 8. С. 3-21. 4. К о р ш у н о в Л.Г., Ч е р н е н к о Н.Л. // Трение и износ. 1984. Т. 5. № 1. С. 106-112. 5. С и л ь м а н Г.И. // МиТОМ. 2006. № 1. С. 3-7. 6. И в а н о в Ю.Ф., А л е ш и н а Е.А., К о л у б а е в Е.А. и др. // Физическая мезомеханика. 2006. Т. 9. № 6. С. 83-90. 7. К о л у б а е в Е.А., К о л у б а е в А.В., С и з о в а О.В. и др. // Физическая мезомеханика. 2005. Т. 8. № 4. С. 49-57. 8. К л и м е н о в В.А., И в а н о в Ю.Ф., П е р е в а л о в а О.Б. и др. // Физика и химия обработки материалов. 2001. № 1. С. 90-97.

I am deeply grateful to my supervisor, Prof. Dr. Marcus Müller, for his indispensable support on my way to the graduation. His keen sense of fundamental physical processes has constantly guided me and made possible to realize this work. I would also like to expresses my gratitude to Prof. Dr. Dmitry Bedrov from the University of Utah (USA) for close and fruitful collaboration as well as for providing useful insights into the self-assembly of alkyl-based surfactants on liquid mercury, which have substantially accelerated the completion of the current work. Moreover, the useful and stimulating discussions with my colleagues from the Technion (Israel), Boris Haimov and Boaz Pokroy, who performed the optical tensiometry experiments, are greatly acknowledged.I also thank all the members of our research group for their support and time spent together in Göttingen.The financial support from the Volkswagen Foundation within the joint German-Israeli program under the Grant VW-ZN2726 is highly acknowledged. The computational resources from the GWDG Göttingen, the HLRN Hannover/Berlin, and the JSC Jülich, Germany are gratefully acknowledged as well.I devote this work to my parents, whose love and care have been always accompanying me.