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\begin{document} |
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%\bibliographystyle{aps} |
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\title{Spontaneous Corrugation of Dipolar Membranes} |
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\author{Xiuquan Sun and J. Daniel Gezelter} |
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\email[E-mail:]{gezelter@nd.edu} |
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\affiliation{Department of Chemistry and Biochemistry,\\ |
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University of Notre Dame, \\ |
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Notre Dame, Indiana 46556} |
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\date{\today} |
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\begin{abstract} |
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We present a simple model for dipolar elastic membranes that gives |
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lattice-bound point dipoles complete orientational freedom as well as |
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translational freedom along one coordinate (out of the plane of the |
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membrane). There is an additional harmonic term which binds each of |
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the dipoles to the six nearest neighbors on either triangular or |
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distorted lattices. The translational freedom of the dipoles allows |
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triangular lattices to find states that break out of the normal |
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orientational disorder of frustrated configurations and which are |
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stabilized by long-range anti-ferroelectric ordering. In order to |
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break out of the frustrated states, the dipolar membranes form |
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corrugated or ``rippled'' phases that make the lattices effectively |
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non-triangular. We observe three common features of the corrugated |
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dipolar membranes: 1) the corrugated phases develop easily when hosted |
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on triangular lattices, 2) the wave vectors for the surface ripples |
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are always found to be perpendicular to the dipole director axis, and |
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3) on triangular lattices, the dipole director axis is found to be |
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parallel to any of the three equivalent lattice directions. |
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\end{abstract} |
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\pacs{68.03.Hj, 82.20.Wt} |
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\maketitle |
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\section{Introduction} |
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\label{Int} |
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The properties of polymeric membranes are known to depend sensitively |
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on the details of the internal interactions between the constituent |
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monomers. A flexible membrane will always have a competition between |
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the energy of curvature and the in-plane stretching energy and will be |
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able to buckle in certain limits of surface tension and |
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temperature.\cite{Safran94} The buckling can be non-specific and |
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centered at dislocation~\cite{Seung1988} or grain-boundary |
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defects,\cite{Carraro1993} or it can be directional and cause long |
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``roof-tile'' or tube-like structures to appear in |
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partially-polymerized phospholipid vesicles.\cite{Mutz1991} |
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|
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One would expect that anisotropic local interactions could lead to |
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interesting properties of the buckled membrane. We report here on the |
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buckling behavior of a membrane composed of harmonically-bound, but |
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freely-rotating electrostatic dipoles. The dipoles have strongly |
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anisotropic local interactions and the membrane exhibits coupling |
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between the buckling and the long-range ordering of the dipoles. |
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|
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Buckling behavior in liquid crystalline and biological membranes is a |
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well-known phenomenon. Relatively pure phosphatidylcholine (PC) |
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bilayers form a corrugated or ``rippled'' phase ($P_{\beta'}$) which |
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appears as an intermediate phase between the gel ($L_\beta$) and fluid |
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($L_{\alpha}$) phases. The $P_{\beta'}$ phase has attracted |
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substantial experimental interest over the past 30 years. Most |
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structural information of the ripple phase has been obtained by the |
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X-ray diffraction~\cite{Sun96,Katsaras00} and freeze-fracture electron |
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microscopy (FFEM).~\cite{Copeland80,Meyer96} Recently, Kaasgaard {\it |
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et al.} used atomic force microscopy (AFM) to observe ripple phase |
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morphology in bilayers supported on mica.~\cite{Kaasgaard03} The |
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experimental results provide strong support for a 2-dimensional |
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triangular packing lattice of the lipid molecules within the ripple |
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phase. This is a notable change from the observed lipid packing |
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within the gel phase.~\cite{Cevc87} There have been a number of |
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theoretical |
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approaches~\cite{Marder84,Goldstein88,McCullough90,Lubensky93,Misbah98,Heimburg00,Kubica02,Bannerjee02} |
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(and some heroic |
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simulations~\cite{Ayton02,Jiang04,Brannigan04a,deVries05,deJoannis06}) |
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undertaken to try to explain this phase, but to date, none have looked |
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specifically at the contribution of the dipolar character of the lipid |
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head groups towards this corrugation. Lipid chain interdigitation |
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certainly plays a major role, and the structures of the ripple phase |
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are highly ordered. The model we investigate here lacks chain |
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interdigitation (as well as the chains themselves!) and will not be |
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detailed enough to rule in favor of (or against) any of these |
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explanations for the $P_{\beta'}$ phase. |
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Membranes containing electrostatic dipoles can also exhibit the |
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flexoelectric effect,\cite{Todorova2004,Harden2006,Petrov2006} which |
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is the ability of mechanical deformations to result in electrostatic |
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organization of the membrane. This phenomenon is a curvature-induced |
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membrane polarization which can lead to potential differences across a |
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membrane. Reverse flexoelectric behavior (in which applied currents |
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effect membrane curvature) has also been observed. Explanations of |
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the details of these effects have typically utilized membrane |
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polarization perpendicular to the face of the |
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membrane,\cite{Petrov2006} and the effect has been observed in both |
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biological,\cite{Raphael2000} bent-core liquid |
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crystalline,\cite{Harden2006} and polymer-dispersed liquid crystalline |
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membranes.\cite{Todorova2004} |
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The problem with using atomistic and even coarse-grained approaches to |
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study membrane buckling phenomena is that only a relatively small |
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number of periods of the corrugation (i.e. one or two) can be |
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realistically simulated given current technology. Also, simulations |
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of lipid bilayers are traditionally carried out with periodic boundary |
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conditions in two or three dimensions and these have the potential to |
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enhance the periodicity of the system at that wavelength. To avoid |
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this pitfall, we are using a model which allows us to have |
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sufficiently large systems so that we are not causing artificial |
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corrugation through the use of periodic boundary conditions. |
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|
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The simplest dipolar membrane is one in which the dipoles are located |
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on fixed lattice sites. Ferroelectric states (with long-range dipolar |
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order) can be observed in dipolar systems with non-triangular |
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packings. However, {\em triangularly}-packed 2-D dipolar systems are |
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inherently frustrated and one would expect a dipolar-disordered phase |
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to be the lowest free energy |
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configuration.\cite{Toulouse1977,Marland1979} Dipolar lattices already |
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have rich phase behavior, but in order to allow the membrane to |
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buckle, a single degree of freedom (translation normal to the membrane |
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face) must be added to each of the dipoles. It would also be possible |
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to allow complete translational freedom. This approach |
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is similar in character to a number of elastic Ising models that have |
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been developed to explain interesting mechanical properties in |
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magnetic alloys.\cite{Renard1966,Zhu2005,Zhu2006,Jiang2006} |
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What we present here is an attempt to find the simplest dipolar model |
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which will exhibit buckling behavior. We are using a modified XYZ |
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lattice model; details of the model can be found in section |
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\ref{sec:model}, results of Monte Carlo simulations using this model |
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are presented in section |
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\ref{sec:results}, and section \ref{sec:discussion} contains our conclusions. |
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\section{2-D Dipolar Membrane} |
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\label{sec:model} |
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The point of developing this model was to arrive at the simplest |
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possible theoretical model which could exhibit spontaneous corrugation |
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of a two-dimensional dipolar medium. Since molecules in polymerized |
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membranes and in the $P_{\beta'}$ ripple phase have limited |
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translational freedom, we have chosen a lattice to support the dipoles |
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in the x-y plane. The lattice may be either triangular (lattice |
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constants $a/b = |
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\sqrt{3}$) or distorted. However, each dipole has 3 degrees of |
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freedom. They may move freely {\em out} of the x-y plane (along the |
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$z$ axis), and they have complete orientational freedom ($0 <= \theta |
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<= \pi$, $0 <= \phi < 2 |
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\pi$). This is essentially a modified X-Y-Z model with translational |
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freedom along the z-axis. |
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The potential energy of the system, |
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\begin{eqnarray} |
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V = \sum_i & & \left( \sum_{j>i} \frac{|\mu|^2}{4\pi \epsilon_0 r_{ij}^3} \left[ |
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{\mathbf{\hat u}_i} \cdot {\mathbf{\hat u}_j} - |
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3({\mathbf{\hat u}_i} \cdot {\mathbf{\hat |
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r}_{ij}})({\mathbf{\hat u}_j} \cdot {\mathbf{\hat r}_{ij}})\right] |
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\right. \nonumber \\ |
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& & \left. + \sum_{j \in NN_i}^6 \frac{k_r}{2}\left( |
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r_{ij}-\sigma \right)^2 \right) |
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\label{eq:pot} |
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\end{eqnarray} |
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In this potential, $\mathbf{\hat u}_i$ is the unit vector pointing |
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along dipole $i$ and $\mathbf{\hat r}_{ij}$ is the unit vector |
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pointing along the inter-dipole vector $\mathbf{r}_{ij}$. The entire |
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potential is governed by three parameters, the dipolar strength |
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($\mu$), the harmonic spring constant ($k_r$) and the preferred |
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intermolecular spacing ($\sigma$). In practice, we set the value of |
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$\sigma$ to the average inter-molecular spacing from the planar |
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lattice, yielding a potential model that has only two parameters for a |
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particular choice of lattice constants $a$ (along the $x$-axis) and |
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$b$ (along the $y$-axis). We also define a set of reduced parameters |
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based on the length scale ($\sigma$) and the energy of the harmonic |
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potential at a deformation of 2 $\sigma$ ($\epsilon = k_r \sigma^2 / |
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2$). Using these two constants, we perform our calculations using |
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reduced distances, ($r^{*} = r / \sigma$), temperatures ($T^{*} = 2 |
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k_B T / k_r \sigma^2$), densities ($\rho^{*} = N \sigma^2 / L_x L_y$), |
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and dipole moments ($\mu^{*} = \mu / \sqrt{4 \pi \epsilon_0 \sigma^5 |
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k_r / 2}$). It should be noted that the density ($\rho^{*}$) depends |
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only on the mean particle spacing in the $x-y$ plane; the lattice is |
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fully populated. |
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To investigate the phase behavior of this model, we have performed a |
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series of Metropolis Monte Carlo simulations of moderately-sized (34.3 |
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$\sigma$ on a side) patches of membrane hosted on both triangular |
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($\gamma = a/b = \sqrt{3}$) and distorted ($\gamma \neq \sqrt{3}$) |
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lattices. The linear extent of one edge of the monolayer was $20 a$ |
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and the system was kept roughly square. The average distance that |
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coplanar dipoles were positioned from their six nearest neighbors was |
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1 $\sigma$ (on both triangular and distorted lattices). Typical |
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system sizes were 1360 dipoles for the triangular lattices and |
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840-2800 dipoles for the distorted lattices. Two-dimensional periodic |
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boundary conditions were used, and the cutoff for the dipole-dipole |
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interaction was set to 4.3 $\sigma$. This cutoff is roughly 2.5 times |
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the typical real-space electrostatic cutoff for molecular systems. |
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Since dipole-dipole interactions decay rapidly with distance, and |
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since the intrinsic three-dimensional periodicity of the Ewald sum can |
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give artifacts in 2-d systems, we have chosen not to use it in these |
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calculations. Although the Ewald sum has been reformulated to handle |
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2-D systems,\cite{Parry75,Parry76,Heyes77,deLeeuw79,Rhee89} these |
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methods are computationally expensive,\cite{Spohr97,Yeh99} and are not |
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necessary in this case. All parameters ($T^{*}$, $\mu^{*}$, and |
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$\gamma$) were varied systematically to study the effects of these |
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parameters on the formation of ripple-like phases. |
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\section{Results and Analysis} |
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\label{sec:results} |
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\subsection{Dipolar Ordering and Coexistence Temperatures} |
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The principal method for observing the orientational ordering |
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transition in dipolar systems is the $P_2$ order parameter (defined as |
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$1.5 \times \lambda_{max}$, where $\lambda_{max}$ is the largest |
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eigenvalue of the matrix, |
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\begin{equation} |
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{\mathsf{S}} = \frac{1}{N} \sum_i \left( |
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\begin{array}{ccc} |
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u^{x}_i u^{x}_i-\frac{1}{3} & u^{x}_i u^{y}_i & u^{x}_i u^{z}_i \\ |
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u^{y}_i u^{x}_i & u^{y}_i u^{y}_i -\frac{1}{3} & u^{y}_i u^{z}_i \\ |
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u^{z}_i u^{x}_i & u^{z}_i u^{y}_i & u^{z}_i u^{z}_i -\frac{1}{3} |
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\end{array} \right). |
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\label{eq:opmatrix} |
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\end{equation} |
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Here $u^{\alpha}_i$ is the $\alpha=x,y,z$ component of the unit vector |
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for dipole $i$. $P_2$ will be $1.0$ for a perfectly-ordered system |
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and near $0$ for a randomized system. Note that this order parameter |
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is {\em not} equal to the polarization of the system. For example, |
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the polarization of the perfect anti-ferroelectric system is $0$, but |
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$P_2$ for an anti-ferroelectric system is $1$. The eigenvector of |
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$\mathsf{S}$ corresponding to the largest eigenvalue is familiar as |
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the director axis, which can be used to determine a privileged dipolar |
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axis for dipole-ordered systems. The top panel in Fig. \ref{phase} |
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shows the values of $P_2$ as a function of temperature for both |
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triangular ($\gamma = 1.732$) and distorted ($\gamma=1.875$) |
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lattices. |
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\begin{figure} |
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\includegraphics[width=\linewidth]{phase} |
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\caption{\label{phase} Top panel: The $P_2$ dipolar order parameter as |
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a function of temperature for both triangular ($\gamma = 1.732$) and |
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distorted ($\gamma = 1.875$) lattices. Bottom Panel: The phase |
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diagram for the dipolar membrane model. The line denotes the division |
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between the dipolar ordered (anti-ferroelectric) and disordered phases. |
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An enlarged view near the triangular lattice is shown inset.} |
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\end{figure} |
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There is a clear order-disorder transition in evidence from this data. |
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Both the triangular and distorted lattices have dipolar-ordered |
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low-temperature phases, and orientationally-disordered high |
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temperature phases. The coexistence temperature for the triangular |
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lattice is significantly lower than for the distorted lattices, and |
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the bulk polarization is approximately $0$ for both dipolar ordered |
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and disordered phases. This gives strong evidence that the dipolar |
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ordered phase is anti-ferroelectric. We have verified that this |
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dipolar ordering transition is not a function of system size by |
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performing identical calculations with systems twice as large. The |
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transition is equally smooth at all system sizes that were studied. |
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Additionally, we have repeated the Monte Carlo simulations over a wide |
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range of lattice ratios ($\gamma$) to generate a dipolar |
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order/disorder phase diagram. The bottom panel in Fig. \ref{phase} |
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shows that the triangular lattice is a low-temperature cusp in the |
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$T^{*}-\gamma$ phase diagram. |
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This phase diagram is remarkable in that it shows an |
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anti-ferroelectric phase near $\gamma=1.732$ where one would expect |
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lattice frustration to result in disordered phases at all |
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temperatures. Observations of the configurations in this phase show |
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clearly that the system has accomplished dipolar ordering by forming |
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large ripple-like structures. We have observed anti-ferroelectric |
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ordering in all three of the equivalent directions on the triangular |
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lattice, and the dipoles have been observed to organize perpendicular |
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to the membrane normal (in the plane of the membrane). It is |
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particularly interesting to note that the ripple-like structures have |
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also been observed to propagate in the three equivalent directions on |
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the lattice, but the {\em direction of ripple propagation is always |
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perpendicular to the dipole director axis}. A snapshot of a typical |
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anti-ferroelectric rippled structure is shown in |
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Fig. \ref{fig:snapshot}. |
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|
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\begin{figure} |
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\includegraphics[width=\linewidth]{snapshot} |
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\caption{\label{fig:snapshot} Top and Side views of a representative |
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configuration for the dipolar ordered phase supported on the |
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triangular lattice. Note the anti-ferroelectric ordering and the long |
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wavelength buckling of the membrane. Dipolar ordering has been |
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observed in all three equivalent directions on the triangular lattice, |
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and the ripple direction is always perpendicular to the director axis |
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for the dipoles.} |
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\end{figure} |
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|
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Although the snapshot in Fig. \ref{fig:snapshot} gives the appearance |
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of three-row stair-like structures, these appear to be transient. On |
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average, the corrugation of the membrane is a relatively smooth, |
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long-wavelength phenomenon, with occasional steep drops between |
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adjacent lines of anti-aligned dipoles. |
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|
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The height-dipole correlation function ($C_{\textrm{hd}}(r, \cos |
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\theta)$) makes the connection between dipolar ordering and the wave |
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vector of the ripple even more explicit. $C_{\textrm{hd}}(r, \cos |
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\theta)$ is an angle-dependent pair distribution function. The angle |
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($\theta$) is the angle between the intermolecular vector |
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$\vec{r}_{ij}$ and direction of dipole $i$, |
308 |
xsun |
3097 |
\begin{equation} |
309 |
gezelter |
3101 |
C_{\textrm{hd}} = \frac{\langle \frac{1}{n(r)} \sum_{i}\sum_{j>i} |
310 |
|
|
h_i \cdot h_j \delta(r - r_{ij}) \delta(\cos \theta_{ij} - |
311 |
gezelter |
3098 |
\cos \theta)\rangle} {\langle h^2 \rangle} |
312 |
xsun |
3097 |
\end{equation} |
313 |
|
|
where $\cos \theta_{ij} = \hat{\mu}_{i} \cdot \hat{r}_{ij}$ and |
314 |
gezelter |
3101 |
$\hat{r}_{ij} = \vec{r}_{ij} / r_{ij}$. $n(r)$ is the number of |
315 |
|
|
dipoles found in a cylindrical shell between $r$ and $r+\delta r$ of |
316 |
|
|
the central particle. Fig. \ref{fig:CrossCorrelation} shows contours |
317 |
|
|
of this correlation function for both anti-ferroelectric, rippled |
318 |
|
|
membranes as well as for the dipole-disordered portion of the phase |
319 |
|
|
diagram. |
320 |
xsun |
3097 |
|
321 |
gezelter |
3098 |
\begin{figure} |
322 |
|
|
\includegraphics[width=\linewidth]{hdc} |
323 |
|
|
\caption{\label{fig:CrossCorrelation} Contours of the height-dipole |
324 |
|
|
correlation function as a function of the dot product between the |
325 |
|
|
dipole ($\hat{\mu}$) and inter-dipole separation vector ($\hat{r}$) |
326 |
|
|
and the distance ($r$) between the dipoles. Perfect height |
327 |
|
|
correlation (contours approaching 1) are present in the ordered phase |
328 |
|
|
when the two dipoles are in the same head-to-tail line. |
329 |
xsun |
3097 |
Anti-correlation (contours below 0) is only seen when the inter-dipole |
330 |
gezelter |
3098 |
vector is perpendicular to the dipoles. In the dipole-disordered |
331 |
|
|
portion of the phase diagram, there is only weak correlation in the |
332 |
|
|
dipole direction and this correlation decays rapidly to zero for |
333 |
|
|
intermolecular vectors that are not dipole-aligned.} |
334 |
xsun |
3097 |
\end{figure} |
335 |
|
|
|
336 |
gezelter |
3101 |
The height-dipole correlation function gives a map of how the topology |
337 |
|
|
of the membrane surface varies with angular deviation around a given |
338 |
|
|
dipole. The upper panel of Fig. \ref{fig:CrossCorrelation} shows that |
339 |
|
|
in the anti-ferroelectric phase, the dipole heights are strongly |
340 |
|
|
correlated for dipoles in head-to-tail arrangements, and this |
341 |
|
|
correlation persists for very long distances (up to 15 $\sigma$). For |
342 |
|
|
portions of the membrane located perpendicular to a given dipole, the |
343 |
|
|
membrane height becomes anti-correlated at distances of 10 $\sigma$. |
344 |
|
|
The correlation function is relatively smooth; there are no steep |
345 |
|
|
jumps or steps, so the stair-like structures in |
346 |
|
|
Fig. \ref{fig:snapshot} are indeed transient and disappear when |
347 |
|
|
averaged over many configurations. In the dipole-disordered phase, |
348 |
|
|
the height-dipole correlation function is relatively flat (and hovers |
349 |
|
|
near zero). The only significant height correlations are for axial |
350 |
|
|
dipoles at very short distances ($r \approx |
351 |
|
|
\sigma$). |
352 |
|
|
|
353 |
gezelter |
3075 |
\subsection{Discriminating Ripples from Thermal Undulations} |
354 |
|
|
|
355 |
|
|
In order to be sure that the structures we have observed are actually |
356 |
|
|
a rippled phase and not simply thermal undulations, we have computed |
357 |
|
|
the undulation spectrum, |
358 |
|
|
\begin{equation} |
359 |
|
|
h(\vec{q}) = A^{-1/2} \int d\vec{r} |
360 |
|
|
h(\vec{r}) e^{-i \vec{q}\cdot\vec{r}} |
361 |
|
|
\end{equation} |
362 |
|
|
where $h(\vec{r})$ is the height of the membrane at location $\vec{r} |
363 |
xsun |
3097 |
= (x,y)$.~\cite{Safran94,Seifert97} In simple (and more complicated) |
364 |
|
|
elastic continuum models, it can shown that in the $NVT$ ensemble, the |
365 |
|
|
absolute value of the undulation spectrum can be written, |
366 |
gezelter |
3075 |
\begin{equation} |
367 |
gezelter |
3098 |
\langle | h(q) |^2 \rangle_{NVT} = \frac{k_B T}{k_c q^4 + |
368 |
|
|
\gamma q^2}, |
369 |
gezelter |
3075 |
\label{eq:fit} |
370 |
|
|
\end{equation} |
371 |
gezelter |
3098 |
where $k_c$ is the bending modulus for the membrane, and $\gamma$ is |
372 |
|
|
the mechanical surface tension.~\cite{Safran94} The systems studied in |
373 |
|
|
this paper have essentially zero bending moduli ($k_c$) and relatively |
374 |
|
|
large mechanical surface tensions ($\gamma$), so a much simpler form |
375 |
|
|
can be written, |
376 |
xsun |
3097 |
\begin{equation} |
377 |
gezelter |
3098 |
\langle | h(q) |^2 \rangle_{NVT} = \frac{k_B T}{\gamma q^2}, |
378 |
xsun |
3097 |
\label{eq:fit2} |
379 |
|
|
\end{equation} |
380 |
gezelter |
3075 |
|
381 |
|
|
The undulation spectrum is computed by superimposing a rectangular |
382 |
|
|
grid on top of the membrane, and by assigning height ($h(\vec{r})$) |
383 |
|
|
values to the grid from the average of all dipoles that fall within a |
384 |
|
|
given $\vec{r}+d\vec{r}$ grid area. Empty grid pixels are assigned |
385 |
|
|
height values by interpolation from the nearest neighbor pixels. A |
386 |
|
|
standard 2-d Fourier transform is then used to obtain $\langle | |
387 |
xsun |
3097 |
h(q)|^2 \rangle$. Alternatively, since the dipoles sit on a Bravais |
388 |
|
|
lattice, one could use the heights of the lattice points themselves as |
389 |
|
|
the grid for the Fourier transform (without interpolating to a square |
390 |
|
|
grid). However, if lateral translational freedom is added to this |
391 |
gezelter |
3098 |
model (a likely extension), an interpolated grid method for computing |
392 |
|
|
undulation spectra will be required. |
393 |
gezelter |
3075 |
|
394 |
xsun |
3097 |
As mentioned above, the best fits to our undulation spectra are |
395 |
gezelter |
3098 |
obtained by setting the value of $k_c$ to 0. In Fig. \ref{fig:fit} we |
396 |
|
|
show typical undulation spectra for two different regions of the phase |
397 |
|
|
diagram along with their fits from the Landau free energy approach |
398 |
|
|
(Eq. \ref{eq:fit2}). In the high-temperature disordered phase, the |
399 |
|
|
Landau fits can be nearly perfect, and from these fits we can estimate |
400 |
|
|
the tension in the surface. In reduced units, typical values of |
401 |
|
|
$\gamma^{*} = \gamma / \epsilon = 2500$ are obtained for the |
402 |
|
|
disordered phase ($\gamma^{*} = 2551.7$ in the top panel of |
403 |
|
|
Fig. \ref{fig:fit}). |
404 |
gezelter |
3075 |
|
405 |
gezelter |
3098 |
Typical values of $\gamma^{*}$ in the dipolar-ordered phase are much |
406 |
|
|
higher than in the dipolar-disordered phase ($\gamma^{*} = 73,538$ in |
407 |
|
|
the lower panel of Fig. \ref{fig:fit}). For the dipolar-ordered |
408 |
|
|
triangular lattice near the coexistence temperature, we also observe |
409 |
|
|
long wavelength undulations that are far outliers to the fits. That |
410 |
|
|
is, the Landau free energy fits are well within error bars for most of |
411 |
|
|
the other points, but can be off by {\em orders of magnitude} for a |
412 |
|
|
few low frequency components. |
413 |
gezelter |
3075 |
|
414 |
|
|
We interpret these outliers as evidence that these low frequency modes |
415 |
|
|
are {\em non-thermal undulations}. We take this as evidence that we |
416 |
|
|
are actually seeing a rippled phase developing in this model system. |
417 |
|
|
|
418 |
gezelter |
3098 |
\begin{figure} |
419 |
|
|
\includegraphics[width=\linewidth]{logFit} |
420 |
|
|
\caption{\label{fig:fit} Evidence that the observed ripples are {\em |
421 |
gezelter |
3101 |
not} thermal undulations is obtained from the 2-d Fourier transform |
422 |
gezelter |
3098 |
$\langle |h^{*}(\vec{q})|^2 \rangle$ of the height profile ($\langle |
423 |
|
|
h^{*}(x,y) \rangle$). Rippled samples show low-wavelength peaks that |
424 |
|
|
are outliers on the Landau free energy fits by an order of magnitude. |
425 |
|
|
Samples exhibiting only thermal undulations fit Eq. \ref{eq:fit} |
426 |
|
|
remarkably well.} |
427 |
gezelter |
3075 |
\end{figure} |
428 |
|
|
|
429 |
|
|
\subsection{Effects of Potential Parameters on Amplitude and Wavelength} |
430 |
|
|
|
431 |
|
|
We have used two different methods to estimate the amplitude and |
432 |
|
|
periodicity of the ripples. The first method requires projection of |
433 |
|
|
the ripples onto a one dimensional rippling axis. Since the rippling |
434 |
|
|
is always perpendicular to the dipole director axis, we can define a |
435 |
|
|
ripple vector as follows. The largest eigenvector, $s_1$, of the |
436 |
|
|
$\mathsf{S}$ matrix in Eq. \ref{eq:opmatrix} is projected onto a |
437 |
|
|
planar director axis, |
438 |
|
|
\begin{equation} |
439 |
|
|
\vec{d} = \left(\begin{array}{c} |
440 |
|
|
\vec{s}_1 \cdot \hat{i} \\ |
441 |
|
|
\vec{s}_1 \cdot \hat{j} \\ |
442 |
|
|
0 |
443 |
|
|
\end{array} \right). |
444 |
|
|
\end{equation} |
445 |
|
|
($\hat{i}$, $\hat{j}$ and $\hat{k}$ are unit vectors along the $x$, |
446 |
|
|
$y$, and $z$ axes, respectively.) The rippling axis is in the plane of |
447 |
|
|
the membrane and is perpendicular to the planar director axis, |
448 |
|
|
\begin{equation} |
449 |
|
|
\vec{q}_{\mathrm{rip}} = \vec{d} \times \hat{k} |
450 |
|
|
\end{equation} |
451 |
|
|
We can then find the height profile of the membrane along the ripple |
452 |
|
|
axis by projecting heights of the dipoles to obtain a one-dimensional |
453 |
|
|
height profile, $h(q_{\mathrm{rip}})$. Ripple wavelengths can be |
454 |
|
|
estimated from the largest non-thermal low-frequency component in the |
455 |
gezelter |
3101 |
Fourier transform of $h(q_{\mathrm{rip}})$. Amplitudes can be |
456 |
gezelter |
3075 |
estimated by measuring peak-to-trough distances in |
457 |
|
|
$h(q_{\mathrm{rip}})$ itself. |
458 |
|
|
|
459 |
|
|
A second, more accurate, and simpler method for estimating ripple |
460 |
|
|
shape is to extract the wavelength and height information directly |
461 |
|
|
from the largest non-thermal peak in the undulation spectrum. For |
462 |
|
|
large-amplitude ripples, the two methods give similar results. The |
463 |
|
|
one-dimensional projection method is more prone to noise (particularly |
464 |
xsun |
3097 |
in the amplitude estimates for the distorted lattices). We report |
465 |
gezelter |
3075 |
amplitudes and wavelengths taken directly from the undulation spectrum |
466 |
|
|
below. |
467 |
|
|
|
468 |
xsun |
3097 |
In the triangular lattice ($\gamma = \sqrt{3}$), the rippling is |
469 |
gezelter |
3075 |
observed for temperatures ($T^{*}$) from $61-122$. The wavelength of |
470 |
|
|
the ripples is remarkably stable at 21.4~$\sigma$ for all but the |
471 |
|
|
temperatures closest to the order-disorder transition. At $T^{*} = |
472 |
|
|
122$, the wavelength drops to 17.1~$\sigma$. |
473 |
|
|
|
474 |
|
|
The dependence of the amplitude on temperature is shown in the top |
475 |
|
|
panel of Fig. \ref{fig:Amplitude}. The rippled structures shrink |
476 |
|
|
smoothly as the temperature rises towards the order-disorder |
477 |
|
|
transition. The wavelengths and amplitudes we observe are |
478 |
|
|
surprisingly close to the $\Lambda / 2$ phase observed by Kaasgaard |
479 |
|
|
{\it et al.} in their work on PC-based lipids.\cite{Kaasgaard03} |
480 |
|
|
However, this is coincidental agreement based on a choice of 7~\AA~as |
481 |
|
|
the mean spacing between lipids. |
482 |
|
|
|
483 |
gezelter |
3098 |
\begin{figure} |
484 |
|
|
\includegraphics[width=\linewidth]{properties_sq} |
485 |
|
|
\caption{\label{fig:Amplitude} a) The amplitude $A^{*}$ of the ripples |
486 |
|
|
vs. temperature for a triangular lattice. b) The amplitude $A^{*}$ of |
487 |
|
|
the ripples vs. dipole strength ($\mu^{*}$) for both the triangular |
488 |
|
|
lattice (circles) and distorted lattice (squares). The reduced |
489 |
|
|
temperatures were kept fixed at $T^{*} = 94$ for the triangular |
490 |
|
|
lattice and $T^{*} = 106$ for the distorted lattice (approximately 2/3 |
491 |
|
|
of the order-disorder transition temperature for each lattice).} |
492 |
gezelter |
3075 |
\end{figure} |
493 |
|
|
|
494 |
|
|
The ripples can be made to disappear by increasing the internal |
495 |
gezelter |
3101 |
elastic tension (i.e. by increasing $k_r$ or equivalently, reducing |
496 |
gezelter |
3075 |
the dipole moment). The amplitude of the ripples depends critically |
497 |
|
|
on the strength of the dipole moments ($\mu^{*}$) in Eq. \ref{eq:pot}. |
498 |
|
|
If the dipoles are weakened substantially (below $\mu^{*}$ = 20) at a |
499 |
|
|
fixed temperature of 94, the membrane loses dipolar ordering |
500 |
|
|
and the ripple structures. The ripples reach a peak amplitude of |
501 |
|
|
3.7~$\sigma$ at a dipolar strength of 25. We show the dependence |
502 |
|
|
of ripple amplitude on the dipolar strength in |
503 |
|
|
Fig. \ref{fig:Amplitude}. |
504 |
|
|
|
505 |
xsun |
3097 |
\subsection{Distorted lattices} |
506 |
gezelter |
3075 |
|
507 |
|
|
We have also investigated the effect of the lattice geometry by |
508 |
|
|
changing the ratio of lattice constants ($\gamma$) while keeping the |
509 |
gezelter |
3101 |
average nearest-neighbor spacing constant. The anti-ferroelectric state |
510 |
gezelter |
3075 |
is accessible for all $\gamma$ values we have used, although the |
511 |
xsun |
3097 |
distorted triangular lattices prefer a particular director axis due to |
512 |
gezelter |
3075 |
the anisotropy of the lattice. |
513 |
|
|
|
514 |
xsun |
3097 |
Our observation of rippling behavior was not limited to the triangular |
515 |
gezelter |
3101 |
lattices. In distorted lattices the anti-ferroelectric phase can |
516 |
gezelter |
3075 |
develop nearly instantaneously in the Monte Carlo simulations, and |
517 |
|
|
these dipolar-ordered phases tend to be remarkably flat. Whenever |
518 |
xsun |
3097 |
rippling has been observed in these distorted lattices |
519 |
gezelter |
3075 |
(e.g. $\gamma = 1.875$), we see relatively short ripple wavelengths |
520 |
|
|
(14 $\sigma$) and amplitudes of 2.4~$\sigma$. These ripples are |
521 |
|
|
weakly dependent on dipolar strength (see Fig. \ref{fig:Amplitude}), |
522 |
|
|
although below a dipolar strength of $\mu^{*} = 20$, the membrane |
523 |
|
|
loses dipolar ordering and displays only thermal undulations. |
524 |
|
|
|
525 |
|
|
The ripple phase does {\em not} appear at all values of $\gamma$. We |
526 |
|
|
have only observed non-thermal undulations in the range $1.625 < |
527 |
|
|
\gamma < 1.875$. Outside this range, the order-disorder transition in |
528 |
|
|
the dipoles remains, but the ordered dipolar phase has only thermal |
529 |
|
|
undulations. This is one of our strongest pieces of evidence that |
530 |
xsun |
3097 |
rippling is a symmetry-breaking phenomenon for triangular and |
531 |
|
|
nearly-triangular lattices. |
532 |
gezelter |
3075 |
|
533 |
|
|
\subsection{Effects of System Size} |
534 |
|
|
To evaluate the effect of finite system size, we have performed a |
535 |
xsun |
3097 |
series of simulations on the triangular lattice at a reduced |
536 |
gezelter |
3075 |
temperature of 122, which is just below the order-disorder transition |
537 |
|
|
temperature ($T^{*} = 139$). These conditions are in the |
538 |
|
|
dipole-ordered and rippled portion of the phase diagram. These are |
539 |
|
|
also the conditions that should be most susceptible to system size |
540 |
|
|
effects. |
541 |
|
|
|
542 |
gezelter |
3098 |
\begin{figure} |
543 |
|
|
\includegraphics[width=\linewidth]{SystemSize} |
544 |
|
|
\caption{\label{fig:systemsize} The ripple wavelength (top) and |
545 |
|
|
amplitude (bottom) as a function of system size for a triangular |
546 |
|
|
lattice ($\gamma=1.732$) at $T^{*} = 122$.} |
547 |
gezelter |
3075 |
\end{figure} |
548 |
|
|
|
549 |
|
|
There is substantial dependence on system size for small (less than |
550 |
|
|
29~$\sigma$) periodic boxes. Notably, there are resonances apparent |
551 |
|
|
in the ripple amplitudes at box lengths of 17.3 and 29.5 $\sigma$. |
552 |
|
|
For larger systems, the behavior of the ripples appears to have |
553 |
|
|
stabilized and is on a trend to slightly smaller amplitudes (and |
554 |
|
|
slightly longer wavelengths) than were observed from the 34.3 $\sigma$ |
555 |
|
|
box sizes that were used for most of the calculations. |
556 |
|
|
|
557 |
|
|
It is interesting to note that system sizes which are multiples of the |
558 |
|
|
default ripple wavelength can enhance the amplitude of the observed |
559 |
|
|
ripples, but appears to have only a minor effect on the observed |
560 |
|
|
wavelength. It would, of course, be better to use system sizes that |
561 |
|
|
were many multiples of the ripple wavelength to be sure that the |
562 |
|
|
periodic box is not driving the phenomenon, but at the largest system |
563 |
|
|
size studied (70 $\sigma$ $\times$ 70 $\sigma$), the number of dipoles |
564 |
|
|
(5440) made long Monte Carlo simulations prohibitively expensive. |
565 |
|
|
|
566 |
|
|
\section{Discussion} |
567 |
|
|
\label{sec:discussion} |
568 |
|
|
|
569 |
|
|
We have been able to show that a simple dipolar lattice model which |
570 |
|
|
contains only molecular packing (from the lattice), anisotropy (in the |
571 |
gezelter |
3101 |
form of electrostatic dipoles) and a weak elastic tension (in the form |
572 |
gezelter |
3075 |
of a nearest-neighbor harmonic potential) is capable of exhibiting |
573 |
|
|
stable long-wavelength non-thermal surface corrugations. The best |
574 |
|
|
explanation for this behavior is that the ability of the dipoles to |
575 |
|
|
translate out of the plane of the membrane is enough to break the |
576 |
gezelter |
3101 |
symmetry of the triangular lattice and allow the energetic benefit |
577 |
|
|
from the formation of a bulk anti-ferroelectric phase. Were the weak |
578 |
|
|
elastic tension absent from our model, it would be possible for the |
579 |
gezelter |
3075 |
entire lattice to ``tilt'' using $z$-translation. Tilting the lattice |
580 |
xsun |
3097 |
in this way would yield an effectively non-triangular lattice which |
581 |
gezelter |
3101 |
would avoid dipolar frustration altogether. With the elastic tension |
582 |
|
|
in place, bulk tilt causes a large strain, and the least costly way to |
583 |
|
|
release this strain is between two rows of anti-aligned dipoles. |
584 |
|
|
These ``breaks'' will result in rippled or sawtooth patterns in the |
585 |
|
|
membrane, and allow small stripes of membrane to form |
586 |
|
|
anti-ferroelectric regions that are tilted relative to the averaged |
587 |
|
|
membrane normal. |
588 |
gezelter |
3075 |
|
589 |
|
|
Although the dipole-dipole interaction is the major driving force for |
590 |
|
|
the long range orientational ordered state, the formation of the |
591 |
|
|
stable, smooth ripples is a result of the competition between the |
592 |
gezelter |
3101 |
elastic tension and the dipole-dipole interactions. This statement is |
593 |
gezelter |
3075 |
supported by the variation in $\mu^{*}$. Substantially weaker dipoles |
594 |
|
|
relative to the surface tension can cause the corrugated phase to |
595 |
|
|
disappear. |
596 |
|
|
|
597 |
xsun |
3097 |
The packing of the dipoles into a nearly-triangular lattice is clearly |
598 |
gezelter |
3075 |
an important piece of the puzzle. The dipolar head groups of lipid |
599 |
|
|
molecules are sterically (as well as electrostatically) anisotropic, |
600 |
gezelter |
3101 |
and would not pack in triangular arrangements without the steric |
601 |
|
|
interference of adjacent molecular bodies. Since we only see rippled |
602 |
|
|
phases in the neighborhood of $\gamma=\sqrt{3}$, this implies that |
603 |
|
|
even if this dipolar mechanism is the correct explanation for the |
604 |
|
|
ripple phase in realistic bilayers, there would still be a role played |
605 |
|
|
by the lipid chains in the in-plane organization of the triangularly |
606 |
|
|
ordered phases which could support ripples. The present model is |
607 |
|
|
certainly not detailed enough to answer exactly what drives the |
608 |
|
|
formation of the $P_{\beta'}$ phase in real lipids, but suggests some |
609 |
|
|
avenues for further experiments. |
610 |
gezelter |
3075 |
|
611 |
|
|
The most important prediction we can make using the results from this |
612 |
|
|
simple model is that if dipolar ordering is driving the surface |
613 |
|
|
corrugation, the wave vectors for the ripples should always found to |
614 |
|
|
be {\it perpendicular} to the dipole director axis. This prediction |
615 |
|
|
should suggest experimental designs which test whether this is really |
616 |
|
|
true in the phosphatidylcholine $P_{\beta'}$ phases. The dipole |
617 |
|
|
director axis should also be easily computable for the all-atom and |
618 |
|
|
coarse-grained simulations that have been published in the literature. |
619 |
|
|
|
620 |
|
|
Our other observation about the ripple and dipolar directionality is |
621 |
|
|
that the dipole director axis can be found to be parallel to any of |
622 |
xsun |
3097 |
the three equivalent lattice vectors in the triangular lattice. |
623 |
gezelter |
3075 |
Defects in the ordering of the dipoles can cause the dipole director |
624 |
|
|
(and consequently the surface corrugation) of small regions to be |
625 |
|
|
rotated relative to each other by 120$^{\circ}$. This is a similar |
626 |
|
|
behavior to the domain rotation seen in the AFM studies of Kaasgaard |
627 |
|
|
{\it et al.}\cite{Kaasgaard03} |
628 |
|
|
|
629 |
|
|
Although our model is simple, it exhibits some rich and unexpected |
630 |
|
|
behaviors. It would clearly be a closer approximation to the reality |
631 |
|
|
if we allowed greater translational freedom to the dipoles and |
632 |
|
|
replaced the somewhat artificial lattice packing and the harmonic |
633 |
gezelter |
3101 |
elastic tension with more realistic molecular modeling potentials. |
634 |
|
|
What we have done is to present a simple model which exhibits bulk |
635 |
|
|
non-thermal corrugation, and our explanation of this rippling |
636 |
|
|
phenomenon will help us design more accurate molecular models for |
637 |
|
|
corrugated membranes and experiments to test whether rippling is |
638 |
|
|
dipole-driven or not. |
639 |
gezelter |
3098 |
|
640 |
|
|
\begin{acknowledgments} |
641 |
|
|
Support for this project was provided by the National Science |
642 |
|
|
Foundation under grant CHE-0134881. The authors would like to thank |
643 |
|
|
the reviewers for helpful comments. |
644 |
|
|
\end{acknowledgments} |
645 |
|
|
|
646 |
gezelter |
3075 |
\bibliography{ripple} |
647 |
|
|
\end{document} |