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\section{Introduction} |
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In a recent series of experiments, Li, Lieberman, and Hill found some |
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remarkable differences in the coverage of Gold (111) surfaces by a |
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remarkable differences in the coverage of Au (111) surfaces by a |
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related set of silicon phthalocyanines.\cite{Li2001} The molecules |
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come in two basic varieties, the ``octopus,'' which has eight thiol |
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groups distributed around the edge of the molecule, and the |
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(4\%) initial rise in $\theta_{J}$ as a function of particle |
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anisotropy. However, the jamming limit {\it decreases} with |
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increasing particle anisotropy once the length-to-breadth ratio rises |
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above 2. I.e. ellipsoids landing randomly on a surface will, in |
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above 2, \emph{i.e.}~ellipsoids landing randomly on a surface will, in |
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general, cover a smaller surface area than disks. Randomly thrown thin |
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lines cover an even smaller area.\cite{Viot1992b} |
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|
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How, then, can one explain a near-monolayer coverage by the umbrella |
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molecules? There are really two approaches, one static and one |
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dynamic. In this paper, we present a static RSA model with {\em |
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molecules? In this paper, we present a static RSA model with {\em |
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tilted} disks that allows near-monolayer coverage and which can |
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explain the differences in coverage between the octopus and umbrella. |
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In section \ref{rsaSec:model} we outline the model for the two adsorbing |
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the thiol groups. In the continuum case, the landers could attach |
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anywhere on the surface. For the lattice-based RSA simulations, an |
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underlying gold hexagonal closed packed (hcp), lattice was employed. |
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The thiols attach at the interstitial locations between three gold |
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The thiols attach at the three-fold hollow locations between three gold |
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atoms on the Au (111) surface,\cite{Li2001} giving a trigonal (i.e. |
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graphitic) underlying lattice for the RSA simulations that is |
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illustrated in Fig. \ref{rsaFig:hcp_lattice}. The hcp nearest neighbor |
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\begin{figure} |
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\centering |
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\includegraphics[width=\linewidth]{hcp_lattice.eps} |
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\caption[Depiction of the hcp interstitial sites]{The model thiol groups attach at the interstitial sites in |
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\caption[Depiction of the hcp three-fold hollow sites]{The model thiol groups attach at the three-fold hollow sites in |
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the Au (111) surface. These sites are arranged in a graphitic |
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trigonal lattice.} |
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\label{rsaFig:hcp_lattice} |
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was then checked for intersection with both of the umbrella tops. If |
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the line did indeed intersect the tops, then the points of |
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intersection along the line were checked to insure sequential |
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intersection of the two tops. ie. The line most enter then leave the |
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intersection of the two tops. ie. The line must enter then leave the |
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first top before it can enter and leave the second top. These series |
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of tests were demanding of computational resources, and were therefore |
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only attempted if the original handle - projection overlap test had |
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|
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For the on-lattice simulations, the initially chosen location on the |
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plane was used to pick an attachment point from the underlying |
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lattice. I.e. if the initial position and orientation placed one of |
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lattice. Meaning, if the initial position and orientation placed one of |
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the thiol legs within a small distance ($\epsilon = 0.1 \mbox{\AA}$) |
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of one of the interstitial attachment points, the lander was moved so |
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that the thiol leg was directly over the lattice point before checking |
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umbrella molecule simulation, and the octopus model simulation. In |
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the case of the umbrella molecule, the surface coverage was tracked by |
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multiplying the number of succesfully landed particles by the area of |
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its circular top. This number was then divided by the total surfacew |
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its circular top. This number was then divided by the total surface |
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area of the plane, to obtain the fractional coverage. In the case of |
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the umbrella molecule, a scanning probe algorithm was used. Here, a |
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$1\mbox{\AA} \times 1\mbox{\AA}$ probe was scanned along the surface, |
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larger gold surface. |
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|
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Once the system is constrained by the underlying lattice, $\theta_{J}$ |
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drops to 0.5378, showing that the lattice has an almost |
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drops to 0.5378, showing that the lattice has an |
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inconsequential effect on the jamming limit. If the spacing between |
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the interstitial sites were closer to the radius of the landing |
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particles, we would expect a larger effect, but in this case, the |
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Table \ref{rsaTab:coverage}. |
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|
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\begin{table} |
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\caption[RSA experimental comparison]{Ratio of Monolayer Sulfur atoms to Gold surface atoms} |
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\caption{RATIO OF MONOLAYER SULFUR ATOMS TO GOLD SURFACE ATOMS} |
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\label{rsaTab:coverage} |
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\begin{center} |
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\begin{tabular}{|l|l|l|} |