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%\url{www.pnas.org/cgi/doi/10.1073/pnas.0709640104} |
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\copyrightyear{2014} |
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\issuedate{Issue Date} |
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\begin{document} |
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\title{Supporting Information for: \\ |
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The different facets of ice have different hydrophilicities: Friction at water / |
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ice-I\textsubscript{h} interfaces} |
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\author{Patrick B. Louden\affil{1}{Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, |
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IN 46556} |
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\and |
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J. Daniel Gezelter\affil{1}{}} |
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\contributor{Submitted to Proceedings of the National Academy of Sciences |
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of the United States of America} |
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\maketitle |
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\begin{article} |
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\section{Overview} |
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The supporting information contains further details about the model |
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construction, analysis methods, and supplies figures that support the |
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data presented in the main text. |
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\section{Construction of the Ice / Water interfaces} |
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Ice I$_\mathrm{h}$ crystallizes in the hexagonal space group |
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P$6_3/mmc$, and common ice crystals form hexagonal plates with the |
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basal face, $\{0~0~0~1\}$, forming the top and bottom of each plate, and |
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the prismatic facet, $\{1~0~\bar{1}~0\}$, forming the sides. In extreme |
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temperatures or low water saturation conditions, ice crystals can |
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easily form as hollow columns, needles and dendrites. These are |
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structures that expose other crystalline facets of the ice to the |
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surroundings. Among the more common facets are the secondary prism, |
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$\{1~1~\bar{2}~0\}$, and pyramidal, $\{2~0~\bar{2}~1\}$, faces. |
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We found it most useful to work with proton-ordered, zero-dipole |
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crystals that expose strips of dangling H-atoms and lone |
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pairs~\cite{Buch:2008fk}. Our structures were created starting from |
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Structure 6 of Hirsch and Ojam\"{a}e's set of orthorhombic |
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representations for ice-I$_{h}$~\cite{Hirsch04}. This crystal |
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structure was cleaved along the four different facets. The exposed |
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face was reoriented normal to the $z$-axis of the simulation cell, and |
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the structures were extended to form large exposed facets in |
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rectangular box geometries. Liquid water boxes were created with |
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identical dimensions (in $x$ and $y$) as the ice, with a $z$ dimension |
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of three times that of the ice block, and a density corresponding to 1 |
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g / cm$^3$. Each of the ice slabs and water boxes were independently |
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equilibrated at a pressure of 1 atm, and the resulting systems were |
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merged by carving out any liquid water molecules within 3 \AA\ of any |
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atoms in the ice slabs. Each of the combined ice/water systems were |
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then equilibrated at 225K, which is the liquid-ice coexistence |
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temperature for SPC/E water~\cite{Bryk02}. Reference |
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\citealp{Louden13} contains a more detailed explanation of the |
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construction of similar ice/water interfaces. The resulting dimensions |
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as well as the number of ice and liquid water molecules contained in |
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each of these systems are shown in Table S1. |
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\section{Further details on the shearing (RNEMD) simulations} |
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All simulations were performed using OpenMD~\cite{OOPSE,openmd}, with a |
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time step of 2 fs and periodic boundary conditions in all three |
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dimensions. Electrostatics were handled using the damped-shifted |
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force real-space electrostatic kernel~\cite{Ewald}. The systems were |
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divided into 100 bins along the $z$-axis for the VSS-RNEMD moves, |
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which were attempted every 2~fs. |
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The interfaces were equilibrated for a total of 10 ns at equilibrium |
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conditions before being exposed to either a shear or thermal gradient. |
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This consisted of 5 ns under a constant temperature (NVT) integrator |
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set to 225~K followed by 5 ns under a microcanonical (NVE) integrator. |
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Weak thermal gradients were allowed to develop using the VSS-RNEMD |
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(NVE) integrator using a small thermal flux ($-2.0\times 10^{-6}$ |
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kcal/mol/\AA$^2$/fs) for a duration of 5 ns to allow the gradient to |
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stabilize. The resulting temperature gradient was $\approx$ 10K over |
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the entire box length, which was sufficient to keep the temperature at |
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the interface within $\pm 1$ K of the 225~K target. |
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Velocity gradients were then imposed using the VSS-RNEMD (NVE) |
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integrator with a range of momentum fluxes. These gradients were |
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allowed to stabilize for 1~ns before data collection started. Once |
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established, four successive 0.5~ns runs were performed for each shear |
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rate. During these simulations, configurations of the system were |
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stored every 1~ps, and statistics on the structure and dynamics in |
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each bin were accumulated throughout the simulations. Although there |
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was some small variation in the measured interfacial width between |
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succcessive runs, no indication of bulk melting or crystallization was |
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observed. That is, no large scale changes in the positions of the top |
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and bottom interfaces occurred during the simulations. |
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\section{A second method for computing contact angles} |
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In addition to the spherical cap method outlined in the main text, a |
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second method for obtaining the contact angle was described by |
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Ruijter, Blake, and Coninck~\cite{Ruijter99}. This method uses a |
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cylindrical averaging of the droplet's density profile. A threshold |
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density of 0.5 g cm\textsuperscript{-3} is used to estimate the |
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location of the edge of the droplet. The $r$ and $z$-dependence of |
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the droplet's edge is then fit to a circle, and the contact angle is |
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computed from the intersection of the fit circle with the $z$-axis |
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location of the solid surface. Again, for each stored configuration, |
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the density profile in a set of annular shells was computed. Due to |
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large density fluctuations close to the ice, all shells located within |
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2 \AA\ of the ice surface were left out of the circular fits. The |
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height of the solid surface ($z_\mathrm{suface}$) along with the best |
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fitting origin ($z_\mathrm{droplet}$) and radius |
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($r_\mathrm{droplet}$) of the droplet can then be used to compute the |
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contact angle, |
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\begin{equation} |
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\theta = 90 + \frac{180}{\pi} \sin^{-1}\left(\frac{z_\mathrm{droplet} - |
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z_\mathrm{surface}}{r_\mathrm{droplet}} \right). |
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\end{equation} |
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\section{Interfacial widths using structural information} |
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To determine the structural widths of the interfaces under shear, each |
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of the systems was divided into 100 bins along the $z$-dimension, and |
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the local tetrahedral order parameter (Eq. 5 in Reference |
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\citealp{Louden13}) was time-averaged in each bin for the duration of |
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the shearing simulation. The spatial dependence of this order |
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parameter, $q(z)$, is the tetrahedrality profile of the interface. |
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The lower panels in figures S2-S5 in the SI show tetrahedrality |
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profiles (in circles) for each of the four interfaces. The $q(z)$ |
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function has a range of $(0,1)$, where a value of unity indicates a |
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perfectly tetrahedral environment. The $q(z)$ for the bulk liquid was |
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found to be $\approx~0.77$, while values of $\approx~0.92$ were more |
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common in the ice. The tetrahedrality profiles were fit using a |
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hyperbolic tangent function (see Eq. 6 in Reference |
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\citealp{Louden13}) designed to smoothly fit the bulk to ice |
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transition while accounting for the weak thermal gradient. In panels |
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$b$ and $c$ of the same figures, the resulting thermal and velocity |
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gradients from an imposed kinetic energy and momentum fluxes can be |
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seen. The vertical dotted lines traversing these figures indicate the |
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midpoints of the interfaces as determined by the tetrahedrality |
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profiles. |
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\section{Interfacial widths using dynamic information} |
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To determine the dynamic widths of the interfaces under shear, each of |
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the systems was divided into bins along the $z$-dimension ($\approx$ 3 |
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\AA\ wide) and $C_2(z,t)$ was computed using only those molecules that |
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were in the bin at the initial time. To compute these correlation |
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functions, each of the 0.5 ns simulations was followed by a shorter |
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200 ps microcanonical (NVE) simulation in which the positions and |
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orientations of every molecule in the system were recorded every 0.1 |
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ps. |
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The time-dependence was fit to a triexponential decay, with three time |
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constants: $\tau_{short}$, measuring the librational motion of the |
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water molecules, $\tau_{middle}$, measuring the timescale for breaking |
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and making of hydrogen bonds, and $\tau_{long}$, corresponding to the |
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translational motion of the water molecules. An additional constant |
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was introduced in the fits to describe molecules in the crystal which |
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do not experience long-time orientational decay. |
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In Figures S6-S9, the $z$-coordinate profiles for the three decay |
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constants, $\tau_{short}$, $\tau_{middle}$, and $\tau_{long}$ for the |
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different interfaces are shown. (Figures S6 \& S7 are new results, |
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and Figures S8 \& S9 are updated plots from Ref \citealp{Louden13}.) |
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In the liquid regions of all four interfaces, we observe |
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$\tau_{middle}$ and $\tau_{long}$ to have approximately consistent |
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values of $3-6$ ps and $30-40$ ps, respectively. Both of these times |
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increase in value approaching the interface. Approaching the |
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interface, we also observe that $\tau_{short}$ decreases from its |
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liquid-state value of $72-76$ fs. The approximate values for the |
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decay constants and the trends approaching the interface match those |
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reported previously for the basal and prismatic interfaces. |
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We have estimated the dynamic interfacial width $d_\mathrm{dyn}$ by |
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fitting the profiles of all the three orientational time constants |
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with an exponential decay to the bulk-liquid behavior, |
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\begin{equation}\label{tauFit} |
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\tau(z)\approx\tau_{liquid}+(\tau_{wall}-\tau_{liquid})e^{-(z-z_{wall})/d_\mathrm{dyn}} |
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\end{equation} |
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where $\tau_{liquid}$ and $\tau_{wall}$ are the liquid and projected |
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wall values of the decay constants, $z_{wall}$ is the location of the |
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interface, as measured by the structural order parameter. These |
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values are shown in table 1 in the main text. Because the bins must be |
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quite wide to obtain reasonable profiles of $C_2(z,t)$, the error |
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estimates for the dynamic widths of the interface are significantly |
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larger than for the structural widths. However, all four interfaces |
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exhibit dynamic widths that are significantly below 1~nm, and are in |
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reasonable agreement with the structural width above. |
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\bibliography{iceWater} |
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\end{article} |
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\begin{table}[h] |
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\centering |
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\caption{Sizes of the droplet and shearing simulations. Cell |
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dimensions are measured in \AA. \label{tab:method}} |
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\begin{tabular}{r|cccc|ccccc} |
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\toprule |
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\multirow{2}{*}{Interface} & \multicolumn{4}{c|}{Droplet} & \multicolumn{5}{c}{Shearing} \\ |
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& $N_\mathrm{ice}$ & $N_\mathrm{droplet}$ & $L_x$ & $L_y$ & $N_\mathrm{ice}$ & $N_\mathrm{liquid}$ & $L_x$ & $L_y$ & $L_z$ \\ |
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\midrule |
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Basal $\{0001\}$ & 12960 & 2048 & 134.70 & 140.04 & 900 & 1846 & 23.87 & 35.83 & 98.64 \\ |
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Pyramidal $\{2~0~\bar{2}~1\}$ & 11136 & 2048 & 143.75 & 121.41 & 1216 & 2203 & 37.47 & 29.50 & 93.02 \\ |
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Prismatic $\{1~0~\bar{1}~0\}$ & 9900 & 2048 & 110.04 & 115.00 & 3000 & 5464 & 35.95 & 35.65 & 205.77 \\ |
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Secondary Prism $\{1~1~\bar{2}~0\}$ & 11520 & 2048 & 146.72 & 124.48 & 3840 & 8176 & 71.87 & 31.66 & 161.55 \\ |
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\bottomrule |
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\end{tabular} |
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\end{table} |
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%S1: contact angle |
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\begin{figure} |
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\includegraphics[width=\linewidth]{ContactAngle} |
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\caption{\label{fig:ContactAngle} The dynamic contact angle of a |
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droplet after approaching each of the four ice facets. The decay to |
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an equilibrium contact angle displays similar dynamics. Although |
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all the surfaces are hydrophilic, the long-time behavior stabilizes |
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to significantly flatter droplets for the basal and pyramidal |
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facets. This suggests a difference in hydrophilicity for these |
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facets compared with the two prismatic facets.} |
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\end{figure} |
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%S2-S5 are the z-rnemd profiles |
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\begin{figure} |
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\includegraphics[width=\linewidth]{Pyr_comic_strip} |
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\caption{\label{fig:pyrComic} Properties of the pyramidal interface |
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being sheared through water at 3.8 ms\textsuperscript{-1}. Lower |
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panel: the local tetrahedral order parameter, $q(z)$, (circles) and |
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the hyperbolic tangent fit (turquoise line). Middle panel: the |
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imposed thermal gradient required to maintain a fixed interfacial |
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temperature of 225 K. Upper panel: the transverse velocity gradient |
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that develops in response to an imposed momentum flux. The vertical |
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dotted lines indicate the locations of the midpoints of the two |
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interfaces.} |
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\end{figure} |
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\begin{figure} |
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\includegraphics[width=\linewidth]{SP_comic_strip} |
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\caption{\label{fig:spComic} The secondary prism interface with a shear |
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rate of 3.5 \ |
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ms\textsuperscript{-1}. Panel descriptions match those in figure \ref{fig:pyrComic}.} |
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\end{figure} |
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\begin{figure} |
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\includegraphics[width=\linewidth]{B_comic_strip} |
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\caption{\label{fig:bComic} The basal interface with a shear |
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rate of 1.3 \ |
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ms\textsuperscript{-1}. Panel descriptions match those in figure \ref{fig:pyrComic}.} |
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\end{figure} |
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\begin{figure} |
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\includegraphics[width=\linewidth]{prismatic_comic_strip} |
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\caption{\label{fig:pComic} The prismatic interface with a shear |
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rate of 2 \ |
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ms\textsuperscript{-1}. Panel descriptions match those in figure \ref{fig:pyrComic}.} |
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\end{figure} |
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%Figures S6-S9 are the z-orientation times |
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\begin{figure} |
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\includegraphics[width=\linewidth]{Pyr-orient} |
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\caption{\label{fig:PyrOrient} The three decay constants of the |
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orientational time correlation function, $C_2(z,t)$, for water as a |
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function of distance from the center of the ice slab. The vertical |
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dashed line indicates the edge of the pyramidal ice slab determined |
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by the local order tetrahedral parameter. The control (circles) and |
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sheared (squares) simulations were fit using shifted-exponential |
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decay (see Eq. 9 in Ref. \citealp{Louden13}).} |
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\end{figure} |
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\begin{figure} |
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\includegraphics[width=\linewidth]{SP-orient} |
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\caption{\label{fig:SPorient} Decay constants for $C_2(z,t)$ at the secondary |
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prism face. Panel descriptions match those in \ref{fig:PyrOrient}.} |
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\end{figure} |
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\begin{figure} |
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\includegraphics[width=\linewidth]{B-orient} |
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\caption{\label{fig:Borient} Decay constants for $C_2(z,t)$ at the basal face. Panel descriptions match those in \ref{fig:PyrOrient}.} |
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\end{figure} |
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\begin{figure} |
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\includegraphics[width=\linewidth]{prismatic-orient} |
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\caption{\label{fig:Porient} Decay constants for $C_2(z,t)$ at the |
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plouden |
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prismatic face. Panel descriptions match those in \ref{fig:PyrOrient}.} |
| 308 |
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\end{figure} |
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|
| 310 |
gezelter |
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|
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\end{document} |
