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# An anchoring transition at surfaces with grafted liquid-crystalline chain molecules

## I Introduction

Nematic liquid crystals are fluids of elongated or oblate particles, which lack translational order, but exhibit long-range orientational order: the molecular axes have a common preferred direction, the director. Surfaces and interfaces align the nearby molecules and thus favor certain director orientations in the bulk . This phenomenon, known as anchoring, plays a key role in the design of liquid-crystal display devices . From a technological point of view, one is particularly interested in tailor-making surfaces which orient a liquid crystal with an arbitrary, well-defined anchoring angle.

In practice, alignment layers are often produced by mechanical rubbing of a polymer coated surface. The technique is simple and successful, yet it has drawbacks: Low tilt angles between the director and the surface normal cannot be achieved easily, and the alignment mechanism is still not understood completely . As an alternative, Halperin and Williams have suggested to use swollen brushes of liquid crystalline polymers as alignment layers. Their idea was to create a competition between the alignment favored by the bare substrate and that enforced by the stretching of polymers in a dense brush. The interplay between the distortion energy of the solvent director field and the conformational entropy of the brush was predicted to trigger a second order anchoring transition between a phase with planar (homogeneous) alignment at low grafting densities and one with tilted alignment at higher grafting densities. The tilt angle can be tuned by adjusting the grafting density.

Subsequently, Peng, Johannsmann and Rühe have undertaken first steps towards an experimental realization of such a scenario. A “grafting-from” technique  allowed to grow thick side-chain liquid crystalline polymer brushes from a substrate covered with surface-attached initiators. A competition as required by Halperin and Williams can be set up by covering the surface between the grafting sites with alkyl chains, which favor homeotropic alignment on the bare substrate. The resulting anchoring behavior has not yet been investigated. However, preliminary miscibility studies have shown that the liquid crystalline brushes can only be swollen to a very limited extent by low molecular weight nematic compounds, even if the latter are chemically similar . One would thus expect that the scenario is altered: The brush and the nematic bulk are presumably separated by an interface, which will contribute significantly to the anchoring properties of the alignment layer.

This aspect of surface anchoring on grafted liquid crystalline chains is explored in the present paper. We study brushes of chains which are too short or too stiff to develop hairpins and the like, and hence mainly follow the director profile. If they attract each other, such short chains exhibit collective tilt. The contribution of the chain entropy to the free energy is of minor importance. Instead, the elastic energy of director distortions competes with a tendency of the chain ends at the surface of the chain layer to stand up, so that more solvent particles can intrude into the interfacial region. As we shall see, the interplay between these two factors leads to a novel anchoring transition between a phase with tilted alignment and one where the layer of grafted chains aligns the bulk vertically (homeotropic alignment), even though the chains inside of the layer are tilted. This is demonstrated with computer simulations and analyzed within a simple theoretical model.

Our paper is organized as follows: We discuss the simulation method and the relevant simulation results in section II. The theoretical model is introduced and analyzed in section III. We summarize and conclude in section IV.

## II Monte Carlo simulations

We have performed Monte Carlo simulations of a fluid of axially symmetric ellipsoidal particles with elongation $`\kappa =\sigma _{\text{end-end}}/\sigma _{\text{side-side}}=3`$. The system was confined between two hard walls, to which chains of the same particles were attached at one end. The grafting points were on a regular square lattice. The simulations were conducted in the $`NPT`$ ensemble, at constant temperature and pressure, and fixed number of particles. Two chain monomers and/or solvent particles with orientations $`𝐮_i`$, $`𝐮_j`$ ($`|𝐮|=1`$), whose centers are separated by a distance vector $`𝐫_{ij}`$, interact through the pair potential

$$V_{ij}=\{\begin{array}{ccc}4ϵ_0(X_{ij}^{12}X_{ij}^6)+ϵ_0\hfill & :& \hfill X_{ij}^6>1/2\\ 0\hfill & :& \hfill \text{otherwise}\end{array}.$$
(1)
Here $`X_{ij}=\sigma _0/(r_{ij}\sigma _{ij}+\sigma _0)`$ is an inverse reduced distance and the shape function

$`\sigma _{ij}(𝐮_i,𝐮_j,\widehat{𝐫}_{ij})=\sigma _0\{1{\displaystyle \frac{\chi }{2}}`$ (3)
$`[{\displaystyle \frac{(𝐮_i\widehat{𝐫}_{ij}+𝐮_j\widehat{𝐫}_{ij})^2}{1+\chi 𝐮_i𝐮_j}}+{\displaystyle \frac{(𝐮_i\widehat{𝐫}_{ij}𝐮_j\widehat{𝐫}_{ij})^2}{1\chi 𝐮_i𝐮_j}}]\}^{1/2}`$
approximates the contact distance in the direction of $`\widehat{𝐫}_{ij}=𝐫_{ij}/r_{ij}`$ of two ellipsoids with orientations $`𝐮_i`$ and $`𝐮_j`$ . The anisotropy parameter $`\chi `$ is defined as $`\chi =(\kappa ^21)/(\kappa ^2+1)`$. A hard core potential prevents the particles from penetrating the walls at $`z=0`$ and $`z=L_z`$:

$$V_W(z)=\{\begin{array}{ccc}0\hfill & :& d_z(\theta )<z<L_zd_z(\theta )\\ \mathrm{}\hfill & :& \text{otherwise}\end{array},$$
(4)
$$\text{with}d_z(\theta )=\sigma _0/2\sqrt{1+\mathrm{cos}^2(\theta )(\kappa ^21)}.$$

The function $`d_z(\theta )`$ is the contact distance between the surface and an ellipsoid of elongation $`\kappa `$ and diameter $`\sigma _0`$ oriented with an angle $`\theta `$ with respect to the surface normal.

Chain monomers are connected by bonds of length $`b`$, which are subject to a spring potential with an equilibrium length $`b=b_0`$ and a logarithmic cutoff at $`|bb_0|=b_s`$.

$$V_S(b)=\{\begin{array}{ccc}\frac{k_s}{2}b_s^2\mathrm{ln}\left(1\frac{(bb_0)^2}{b_s^2}\right)\hfill & :& \hfill |bb_0|<b_s\\ \mathrm{}\hfill & :& \hfill |bb_0|>b_s\end{array}.$$
(5)
The bonds are made stiff and coupled to the orientations of the monomers by virtue of a stiffness potential

$$V_A(\theta _1,\theta _2,\theta _{12})=k_a[\mathrm{\hspace{0.25em}4}\mathrm{cos}(\theta _1)\mathrm{cos}(\theta _2)2\mathrm{cos}(\theta _{12})],$$
(6)
which depends on the angles $`\theta _1`$ and $`\theta _2`$ between the orientation of a monomer and the adjacent bonds, and the angle $`\theta _{12}`$ between the two bonds. The first bond of each chain is attached to one of the surfaces.

We chose the model parameters $`k_s=10ϵ_0/\sigma _0^2`$, $`k_a=10ϵ_0`$, $`b_0=4.\sigma _0`$ and $`b_s=0.8\sigma _0`$. The simulations were performed at the temperature $`T=0.5ϵ_0/k_B`$ and pressure $`P=3ϵ_0/\sigma _0^3`$. This corresponds to a state well in the nematic phase: The transition to the isotropic phase occurs at the pressure $`P=2.3ϵ_0/\sigma _0^3`$. The bulk number density was $`\rho =0.313/\sigma _0^3`$.

We used a rectangular simulation box of size $`L_{}\times L_{}\times L_z`$ with periodic boundary conditions in the $`x`$ and $`y`$ direction and fixed boundary conditions in the $`z`$ direction. The Monte Carlo moves included particle displacements, rescaling of the simulation box in the $`z`$ direction (the lateral box size $`L_{}`$ was kept constant in order to maintain a fixed grafting density), and a special variant of configurational biased Monte Carlo moves , in which chain monomers are turned into solvent particles and new chains are grown from the solvent. Details of this algorithm will be published elsewhere .

We have studied systems with roughly 2000 solvent particles (the numbers varied slightly in the different runs) and up to 242 chains of four monomers in simulation boxes of lateral size $`L_{}=12\sigma _0`$. The length $`L_z`$ of the boxes fluctuated with $`L_z65\sigma _0`$ at the highest grafting density. The walls orient the solvent particles parallel to the surface. We started from an initial configuration where particles all pointed into the $`x`$ direction. This was achieved by applying a strong orienting field over roughly 50.000 Monte Carlo steps. After turning this field off, the system was equilibrated over at least 1 million Monte Carlo steps; data were then collected over 5 million or more Monte Carlo steps.

The results from these simulations for a range of grafting densities $`\mathrm{\Sigma }`$ will be presented in detail elsewhere . Here, we focus on the anchoring effect that is the subject of this paper. Figure 1 shows two configuration snapshots of systems at grafting densities $`\mathrm{\Sigma }=0.34/\sigma _0^2`$ and $`\mathrm{\Sigma }=0.84/\sigma _0^2`$. The grafted chains are tilted in both cases. At the lower grafting density $`\mathrm{\Sigma }=0.34/\sigma _0^2`$, the tilt propagates into the bulk of the film. At $`\mathrm{\Sigma }=0.84/\sigma _0^2`$, the orientation of the liquid crystal outside in the bulk is perpendicular to the surface, even though the chains still retain tilt.

One might suspect an equilibration problem. In order to exclude this possibility, we have prepared an initial configuration in which all particles are oriented in the $`z`$ direction. It relaxes into the same structure as Fig. 1.

The effect can be characterized more quantitatively by inspection of local order parameter profiles. The order tensor of a system of $`n`$ particles is defined by

$$𝐐=\frac{1}{n}\underset{i=1}{\overset{n}{}}(\frac{3}{2}𝐮_i𝐮_i\frac{1}{2}𝐈),$$
(7)
where $`𝐮_i`$ denotes the orientation of the particle $`i`$ as above, $`𝐈`$ the unity matrix, and $``$ the dyadic product.

The largest eigenvalue of this matrix is the nematic order parameter $`S`$ (roughly 0.75 in the bulk of our system), and the corresponding eigenvector is the director $`𝐧`$. In order to obtain profiles of these quantities, we subdivide the system in the $`z`$ direction into slabs of thickness $`\delta z=0.1\sigma _0`$, and determine the order tensor in each slab. Note that the value of $`S`$ is larger in a slab than in the bulk due to the small number of particles in each slab.

Figs. 2 a) and b) show averaged profiles of the order parameter and of the $`z`$-component of the director for the same grafting densities as in Fig. 1. The order parameter varies very little throughout the film; it is slightly larger in the chain region, due to fact that chain monomers have less rotational freedom than solvent particles. The direction of alignment varies much more. Close to the surface, the particles are aligned parallel to the wall. However, the chains reorient the director within a few particle diameters from the surface. Then follows a region of slower changes, where the director gradually stands up. This region is restricted to the inside of the chain layer; further changes outside of the chain layer are small. In the case of $`\mathrm{\Sigma }=0.84/\sigma _0^2`$, the last monomers of the chains are almost perpendicular to the surface, even though the director is tilted inside of the chain region.

To characterize the chain layer further, Figs. 2 also show the density of chains and the density of chain ends (end monomers). A few chain ends are located very close to the substrate at distances $`z=12\sigma _0`$; they belong to chains which lie flat on the surface. The other chain ends are concentrated at the interface between the chain region and the bulk fluid. The higher the grafting density, the more efficiently the chain ends are expelled from the inside of the chain layer towards the chain-bulk interface.

Since the cell width $`L_{}=12\sigma _0`$ is rather small, quantitative details of the curves shown in Fig. 2 are presumably subject to finite size effects. The simulations were very time consuming, and we were not able to consider different system sizes. In the following, we shall focus on the qualitative observation that the chains produce homeotropic alignment beyond a certain grafting density, even though they themselves remain tilted.

## III A Theoretical Model

In this section, we shall propose a simple theoretical model for liquid crystalline chains in a nematic solvent which can explain the phenomenon reported in the previous section.

At first sight, the observation that the director orientation outside of the chain layer differs from that in the chain layer is surprising. The “interface” between the chain layer and the pure solvent seems to orient the particles in a homeotropic way. However, the origin of that anchoring force is not obvious. If one admits the existence of such an aligning force, one is left with the question why the chains are still tilted. In the scenario of Halperin and Williams  the tilt is inherited from the bare substrate, which favors planar anchoring. In the simulations, the rapid director changes in the vicinity of the substrate suggest that the director orientation in the chain layer is largely decoupled from that at the substrate. Alternatively, collective tilt can be induced by attractive interactions between chains . Such interactions can be mediated by solvent particles due to local packing effects, even if the direct interactions are purely repulsive .

Our model is designed to investigate on a simplified level the effect of such an interaction. We describe the chains by smooth differentiable paths $`𝐑(l)`$ of length $`L`$ (wormlike chains ), which follow exactly the director field of the surrounding solvent: $`d𝐑/dl=𝐧(𝐑)`$, and are attached to the surface at one end. The grafting density is measured in terms of a dimensionless area fraction $`\zeta `$, which is defined as the grafting density times the cross section area of one chain. Fluctuations of the director are neglected. Moreover, we do not account for the possibility of hairpins .

The model has the following four key ingredients:

1. The elasticity of the nematic fluid.
2. The translational entropy of the solvent.
3. The interactions between the chains.
4. The anchoring energy of the substrate.

The elastic energy is given by the Frank free energy functional

$`_{\text{Frank}}\{𝐧(𝐫)\}={\displaystyle \frac{1}{2}}{\displaystyle }d𝐫\{K_{11}[𝐧]^2+`$ (9)
$`K_{22}[𝐧(\times 𝐧)]^2+K_{33}[𝐧\times (\times 𝐧)]^2\},`$
with the Frank elastic constants $`K_{11}`$ (splay), $`K_{22}`$ (twist) and $`K_{33}`$ (bend).

The translational entropy of the solvent is calculated within the Flory-Huggins approximation

$$_{\text{solvent}}\{\mathrm{\Phi }(𝐫)\}=\frac{k_BT}{v_s}𝑑𝐫(1\mathrm{\Phi })\mathrm{ln}(1\mathrm{\Phi }).$$
(10)
Here $`k_B`$ is the Boltzmann factor, $`T`$ the temperature, $`v_S`$ the volume occupied by a solvent particle, and $`\mathrm{\Phi }(𝐫)`$ the local volume fraction of chain monomers.

The excluded volume interactions between chains are incorporated by the constraint that $`\mathrm{\Phi }(𝐫)`$ must never exceed one. The attractive interactions are described by a quadratic free energy contribution,

$$_{\text{chains}}\{\mathrm{\Phi }(𝐫)\}=\frac{v}{2}𝑑𝐫\mathrm{\Phi }^2,$$
(11)
where $`v`$ is an effective interaction strength. Since the chains are monodisperse and have no hairpins, their ends are located on a smooth, well-defined surface. In the vicinity of that surface, the number of interacting neighbors of a monomer is reduced, which in turn reduces the interaction energy. We account for this by adding a correction term

$$_{\text{surface}}\{\mathrm{\Phi }(𝐫);𝐧(𝐫)\}=v_{\text{surface}}𝑑𝐬\mathrm{\Phi }^2\gamma (\mathrm{\Phi },𝐧,𝐮_𝐬).$$
(12)
The integral $`_{\text{surface}}𝑑𝐬`$ runs over the surface of the chain layer, and $`𝐮_𝐬`$ denotes the unit vector in direction of the surface normal. The function $`\gamma `$ integrates over the fraction of “missing” interaction energy in a region close to the surface. We take $`\gamma `$ to be proportional to the thickness of the affected region, which we calculate as illustrated in Figure 3: $`\gamma a\mathrm{sin}(\theta )`$, where $`\theta `$ is the angle between the monomer orientation $`𝐧`$ and the surface normal $`𝐮_𝐬`$, and $`a`$ the distance between two neighbor chains, $`a1/\sqrt{\mathrm{\Phi }}`$. This yields

$$\gamma (\mathrm{\Phi },𝐧,𝐮_𝐬)=\widehat{\gamma }\mathrm{\Phi }^{1/2}\sqrt{1(𝐧𝐮)^2}.$$
(13)
The proportionality constant $`\widehat{\gamma }`$ depends on the form of the chain interactions and the actual chain packing at the surface, and is presumably of order 1.

The free energy contribution (12), (13) turns out to be essential for the effect that we wish to study. On the other hand, the considerations which led to eqn. (13) may seem somewhat crude and oversimplified. Therefore, we add some comments which justify an ansatz of the form (13) on more general grounds: In an anisotropic system, one clearly expects the missing neighbor contribution (12) at the surface of the chain layer to be anisotropic, i.e., to depend on the angle $`\theta `$ between the surface normal and the director. Since the chains are aligned along the director, interchain interactions take place in directions perpendicular to the director mainly. Hence fewer interactions are missing if the director is perpendicular to the surface, and the missing neighbor contribution should favor small $`\theta `$. The ansatz (13), $`_{\text{surface}}\mathrm{sin}(\theta )`$, ensures this in the simplest possible way. Other expressions which favor small $`\theta `$ lead to similar results.

Finally, the orienting effect of the bare substrate is described by a quadratic potential

$$_{\text{substrate}}\{𝐧(𝐫)\}=W_{\text{substrate}}𝑑𝐬(𝐧𝐮_𝐬)^2.$$
(14)
The surface integral $`𝑑𝐬`$ runs over the surface of the substrate. Other substrate-related free energy contributions, such as missing neighbor effects of the type (12) and solvent mediated interactions between the chains and the substrate are taken to be negligible compared to the anchoring energy (14). Furthermore, we neglect the internal stiffness of chains, and disregard the possibility that the elastic constants may vary locally and depend on the volume fraction occupied by the chains. These contributions can be incorporated in our model in a relatively straightforward way, but at the expense of having more model parameters. The results do not change qualitatively.

Since fluctuations are neglected, quantities vary only in the direction perpendicular to the surface, the $`z`$-direction, and the director $`𝐧`$ does not rotate in the $`xy`$-plane. Inside of the chain layer, the local volume fraction $`\mathrm{\Phi }(z)`$ of the chains is given by $`\mathrm{\Phi }(z)=\zeta /n_z(z)`$. Outside of the chain layer, $`\mathrm{\Phi }(z)`$ is zero and the director is constant. Hence the system can be described entirely in terms of the profile $`n_z(z)`$ inside of the chain layer. The free energy per surface area is given by

$`\{n_z(z)\}`$ $`=`$ $`{\displaystyle _0^H}dz\{{\displaystyle \frac{1}{2}}({\displaystyle \frac{dn_z}{dz}})^2(K_{11}+K_{33}{\displaystyle \frac{n_z^2}{1n_z^2}})`$ (17)
$`+{\displaystyle \frac{k_BT}{v_s}}(1{\displaystyle \frac{\zeta }{n_z}})\mathrm{ln}(1{\displaystyle \frac{\zeta }{n_z}}){\displaystyle \frac{v}{2}}({\displaystyle \frac{\zeta }{n_z}})^2\}`$
$`+Wn_z^2|_{z=0}+\widehat{\gamma }v\sqrt{\zeta ^3}\sqrt{{\displaystyle \frac{1n_z^2}{n_z^3}}}|_{z=H}.`$
The height $`H`$ of the chain layer is determined implicitly by the requirement $`L=_0^H𝑑z/n_z(z)`$.

For practical calculations, it is convenient to perform the variable transformation $`dl=dz/n_z(z)`$, i.e., to consider variations along the chains rather than variations in the $`z`$-direction. Furthermore, we define the units of length and energy  such that $`(K_{11}+K_{33})/2=1`$ and $`k_BT/v_s=1`$, and introduce the notation $`\delta K=(K_{33}K_{11})/(K_{33}+K_{11})`$. The free energy per surface area is then expressed as a functional of the profile $`\theta (l)=\mathrm{arccos}(n_z(l))`$ of the angle $`\theta `$ between $`𝐧`$ and the surface normal:

$`\{\theta (l)\}`$ $`=`$ $`{\displaystyle _0^L}𝑑l\left\{{\displaystyle \frac{1}{2}}C(l)({\displaystyle \frac{d\theta }{dl}})^2+U(\theta )\right\}`$ (19)
$`+W\mathrm{cos}^2(\theta )|_{l=0}+\widehat{\gamma }v\sqrt{\zeta ^3}{\displaystyle \frac{\mathrm{sin}(\theta )}{\sqrt{\mathrm{cos}^3(\theta )}}}|_{l=L},`$
with

$`C(\theta )`$ $`=`$ $`{\displaystyle \frac{1}{\mathrm{cos}(\theta )}}(1+\delta K\mathrm{cos}(2\theta ))`$ (20)
$`U(\theta )`$ $`=`$ $`\zeta \widehat{U}({\displaystyle \frac{\mathrm{cos}(\theta )}{\zeta }})`$ (21)
$$\text{and}\widehat{U}(x)=(x1)\mathrm{ln}(1\frac{1}{x})\frac{v}{2x}.$$

Minimizing this functional yields the Euler-Lagrange equation

$$C\frac{d^2\theta }{dl^2}+\frac{1}{2}(\frac{d\theta }{dl})^2\frac{dC}{d\theta }\frac{dU}{d\theta }=0.$$
(22)
and the boundary conditions

$`l=0`$ $`:`$ $`C(\theta ){\displaystyle \frac{d\theta }{dl}}=2W\mathrm{cos}(\theta )\mathrm{sin}(\theta )`$ (24)
$`\text{or}\theta =\mathrm{arccos}(\zeta )`$
$`l=L`$ $`:`$ $`C(\theta ){\displaystyle \frac{d\theta }{dl}}=\widehat{\gamma }v\sqrt{\zeta ^3}{\displaystyle \frac{1+3/2\mathrm{tan}^2(\theta )}{\sqrt{\mathrm{cos}(\theta )}}}`$ (26)
$`\text{or}\theta =0.`$
Eqn. (22) describes the trajectory of a particle in space $`\theta `$ and time $`l`$ with a position dependent mass $`C(\theta )`$, which moves in the potential $`U(\theta )`$. The boundary conditions pull the particle in the direction of large $`\theta `$ at $`l=L`$ and in the direction of small $`\theta `$ at $`l=0`$. Hence the profile of $`\theta `$ decreases monotonically with $`l`$. The anchoring angle on the chain layer is given by $`\theta (L)`$.

The properties of the model are most easily discussed in the limit of long chains, $`L\mathrm{}`$. The two boundaries of the chain layer at $`l=0`$ and $`l=L`$ are then decoupled, and there exists a region inside of the chain layer in which $`\theta (l)`$ is constant, $`\theta (l)\overline{\theta }`$. The stationary angle $`\overline{\theta }`$ is the angle where $`U(\theta )`$ has its minimum. It depends on the grafting density $`\zeta `$ and the chain interaction parameter $`v`$. If $`v>1`$, the chains exhibits a continuous transition from an untilted state at large $`\zeta `$ to a tilted state at $`\zeta <\zeta _c(v)`$, where $`\zeta _c(v)`$ is determined by the implicit equation

$$v=\frac{2}{\zeta _c(v)^2}\{\zeta _c(v)+\mathrm{ln}[1\zeta _c(v)]\}.$$
(27)
In the vicinity of the phase transition, at $`\zeta \zeta _c(v)`$, the potential $`U(\theta )`$ can be expanded like

$$U(\theta )=\text{const.}\frac{1}{2}(\zeta _c\zeta )b(\zeta _c)\theta ^2+\frac{1}{8}\zeta _cb(\zeta _c)\theta ^4$$
(28)
with $`b(\zeta )=(2\zeta )/(1\zeta )+2/\zeta \mathrm{ln}(1\zeta )`$, and the minimum is found at

$$\overline{\theta }=\sqrt{2(\zeta _c\zeta )/\zeta _c}.$$
(29)
A necessary criterion for the validity of the expansion is obviously $`\mathrm{\Phi }=\zeta /\mathrm{cos}(\overline{\theta })<1`$, which is fulfilled if

$$\zeta _c\zeta <2\zeta _c\mathrm{arccos}^2(\zeta _c).$$
(30)
Far from the transition, $`U(\theta )`$ takes its minimum close to the maximum value of $`\theta `$ at $`\mathrm{cos}(\overline{\theta })/\zeta 1`$ and one obtains

$$U(0)U(\overline{\theta })=(1\zeta )[\mathrm{ln}(1\zeta )+v\zeta /2].$$
(31)
In the case $`L\mathrm{}`$, the anchoring angle $`\theta (L)`$ of the nematic film at the surface of the chain layer does not depend on the anchoring strength $`W`$ of the substrate. Exploiting the integration constant of the Euler-Lagrange equation (22), $`U(\theta )\frac{1}{2}C(\theta )(\frac{d\theta }{dl})^2`$ const. $`=U(\overline{\theta })`$, one can rewrite the boundary condition (26) at $`l=L`$ as

$$U(\theta (L))U(\overline{\theta })=g(\theta )\text{or}\theta (L)=0.$$
(32)
$$\text{with}g(\theta )=2\widehat{\gamma }^2v^2\zeta ^3\frac{(1+3/2\mathrm{tan}^2(\theta ))^2}{1+\delta K\mathrm{cos}(2\theta )}$$

The problem can be solved graphically as sketched in Fig. 4. Since $`g(\theta )`$ grows monotonically for all $`\delta K<1`$, the curves $`g(\theta )`$ and $`U(\theta )U(\overline{\theta })`$ cross at most at one point in the region $`\theta <\overline{\theta }`$. If such a point exists, it defines the anchoring angle $`\theta (L)`$. Otherwise, the case $`\theta (L)=0`$ applies and the anchoring is homeotropic. The transition between homeotropic and tilted anchoring is continuous. The grafting density at the transition $`\zeta ^{}(v)`$ can be calculated by solving $`U(0)U(\overline{\theta })=g(0)`$ for a given interaction parameter $`v`$. If $`v`$ is small, $`\zeta ^{}(v)`$ is close to the tilting transition $`\zeta _c(v)`$ of the chains, and Eqn. (29) applies. The tilt angle $`\overline{\theta }^{}`$ of the chains at the transition can be approximated by its asymptotic value at small grafting densities $`\zeta ^{}(v)\stackrel{v1}{}0`$. Using Eqns. (27) and expanding $`\mathrm{cos}(\overline{\theta }^{})`$ in powers of $`\overline{\theta }^{}`$, one obtains after some algebra

$$\zeta ^{}(v)\zeta _c(v)/(1+2\widehat{\gamma }\sqrt{3/(1+\delta K)}).$$
(33)
At large $`v`$, $`\zeta ^{}`$ is far from $`\zeta _c`$ and Eqn. (31) leads to

$$\zeta ^{}(v)\sqrt{1+\delta K}/(2\widehat{\gamma }\sqrt{v}).$$
(34)
Fig. 5 shows two examples of phase diagrams for the parameter values $`\widehat{\gamma }/\sqrt{1+\delta K}=0.5`$ and $`0.1`$. We expect that typical values of $`\widehat{\gamma }/\sqrt{1+\delta K}`$ are in that range. At high grafting density $`\zeta `$ and low chain interaction parameter $`v`$, the chains stand upright, perpendicular to the surface. The thin line marks the continuous transition $`\zeta _c(v)`$ to a phase where they tilt collectively. However, the orientation of the director outside of the chain layer still remains perpendicular. Only at grafting densities below a second critical value $`\zeta ^{}(v)<\zeta _c(v)`$ (thick line) do the chains induce tilted alignment in the bulk of the nematic fluid.

In agreement with the observations from computer simulations reported in the previous section II, we thus find a region in $`\zeta v`$ space where the chains are tilted, but nevertheless align the solvent in a homeotropic way. The size of that region increases with $`\widehat{\gamma }`$, i.e., with the amplitude of the (anisotropic) missing neighbor effect at the surface of the chain layer. It is bounded by two continuous phase transitions - one at high grafting density to a phase where both the chains and the adjacent fluid are untilted, and one at low grafting density to a phase where they are both tilted.

So far we have discussed this phenomenon for the limit of long chains, $`L\mathrm{}`$. In systems with shorter chains, the scenario remains qualitatively similar. If the anchoring on the bare substrate is planar ($`W>0`$ in Eqn. (14)), the sharp tilting transition in the chain region is replaced by a smoother crossover from distinctly tilted to roughly perpendicular chain orientation , and the anchoring transition shifts to higher grafting densities. One still finds a region where markedly tilted chains align the nematic solvent in a homeotropic way.

## IV Summary and Discussion

To summarize, we have described a new type of anchoring transition on grafted layers of main-chain liquid-crystalline chain molecules. It is driven by the competition between attractive chain interactions, the translational entropy of the nematic solvent in a region close to the surface of the chain layer, and the elastic energy of the nematic fluid which opposes rapid director changes. Inside of the chain layer, the chain interactions make the chains tilt collectively. Close to the surface, the interactions are reduced, and an increased number of solvent particles enters and swells the chains. As a result, chain ends in the surface region stand up. The anchoring angle imposed by the chains on the adjoining nematic fluid is thus smaller than the actual tilt angle of the chains. Above a critical grafting density $`\zeta ^{}`$, it drops to zero, despite the fact that the chains are still tilted. We have observed this effect in computer simulations of a model system with swollen grafted chains, and rationalized it in terms of a simple theoretical model.

The new anchoring transition is controlled by the grafting density of the chains. In that sense, it is similar to that discussed by Halperin and Williams . However, the phase transition and the underlying mechanism is very different. In the case studied by Halperin and Williams, the chains are long and flexible enough to support many hairpins. The solvent is taken to be very good, i. e., chain monomers effectively repel each other. The transition is driven by an interplay between the conformational entropy of the chains, the anchoring force of the substrate on the solvent, and the elastic energy in the brush. The transition connects a phase with planar anchoring and one with tilted anchoring.

In the present paper, we consider a different regime: The chains are shorter or stiffer, they have no hairpins, and their conformational entropy is negligible. The solvent is not good, chains effectively attract each other and there exists a well-defined interface between the chain layer and the solvent. The anchoring behavior is controlled by the structure of that interface. The influence of the bare substrate is minor. The transition connects a phase with tilted anchoring and one with perpendicular anchoring.

One might ask whether there could be a second transition between planar and tilted anchoring, at a lower grafting density, which would resemble that discussed by Halperin and Williams. Our theoretical model does not predict such a transition. In the simulations, the situation is more complicated. The data indicate the presence of a first order transition, which has nothing to do with hairpins, but is still related to the organization of the chains. This will be described in detail in a separate publication .

Experimentally, one finds that liquid crystalline polymers are not swollen very well by nematic solvents . We thus believe that our effect can be observed in real systems. The grafting density must be high to achieve low anchoring angles $`\theta `$, on the other hand, the chains need not be much longer than their persistence length. Moreover, our results indicate that the grafting density required for the transition decreases with decreasing solvent quality. Brushes with high grafting densities can be prepared with the “grafting from” technique developed by Rühe et al . This technique has been used in the experiments of Peng et al  mentioned in the introduction. However, Peng et al studied brushes with liquid crystalline side chains, where the mesogenic units are preferably oriented perpendicular to the backbone of the chains. The swelling of the brush in the surface region thus promotes planar anchoring, and no transition to homeotropic anchoring can be expected. The effect discussed in the present paper will presumably transpire in a similar experiment with short main-chain liquid-crystalline polymers.

One necessary requirement is of course that the orientation of the chains is homogeneous. This turned out to be a problem experimentally , the brushes tend to exhibit planar multidomains. However, recent work indicates that an appropriate treatment of the bare substrate before growing the brush can force the chains into one monodomain . If brushes could be grown with grafting densities close to the transition density $`\zeta ^{}`$, it would be possible to prepare surfaces which anchor the solvent at any given small tilt angle $`\theta ^{}`$. This would potentially have applications in the design of liquid crystal display devices.

Future theoretical work will have to study in more detail the chain length dependence. The theory presented here has been devised for long chains – for example, they have been described by homogeneous strings – but the chains in the simulations were very short with only four monomer units. Chains in real brushes are usually polydisperse. The influence of polydispersity on the anchoring behavior is not clear. Thus far the analytical model calculations have disregarded the possibility of lateral structure and lateral fluctuations. These will certainly become important for polydisperse brushes and more generally at low grafting densities.

## Acknowledgments

We thank M. P. Allen and K. Binder for useful discussions, and for allowing us to perform a major part of the simulations on the computers of the university of Bristol and the university of Mainz. We have also benefitted from stimulating interactions with D. Johannsmann, J. Rühe and A. Halperin. This work was funded by the German Science Foundation (DFG).


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# Broken symmetries and pattern formation in two-frequency forced Faraday waves

## Abstract

We exploit the presence of approximate (broken) symmetries to obtain general scaling laws governing the process of pattern formation in weakly damped Faraday waves. Specifically, we consider a two-frequency forcing function and trace the effects of time translation, time reversal and Hamiltonian structure for three illustrative examples: hexagons, two-mode superlattices, and two-mode rhomboids. By means of explicit parameter symmetries, we show how the size of various three-wave resonant interactions depends on the frequency ratio $`m`$:$`n`$ and on the relative temporal phase of the two driving terms. These symmetry-based predictions are verified for numerically calculated coefficients, and help explain the results of recent experiments.

preprint: Faraday

Symmetry arguments play a central role in our understanding of pattern formation in nonlinear, nonequilibrium systems. They explain, for example, the ubiquity of simple patterns such as hexagons, squares and stripes observed in widely disparate systems, both in nature and in the laboratory Cross and Hohenberg (1993). Group theory provides the natural language for describing and classifying patterns and, when combined with bifurcation theory, it determines which patterns may result from a symmetry-breaking instability Golubitsky and Shaeffer (1985). It is by now standard practice to invoke symmetry arguments to determine which nonlinear terms are present in the universal amplitude equations that govern the pattern formation processes near onset. The detailed physics is manifest in these amplitude equations only through the numerical values of the coefficients of the nonlinear terms, yet the computation of these coefficients is often an arduous task that must be carried out numerically.

In this letter we develop symmetry arguments in a somewhat nonstandard way, using parameter symmetries (symmetries which act on both amplitudes and parameters; see e.g. Swift (1988)) to determine the dependence of the most important coefficients in the amplitude equations on the parameters of the forcing function and on the damping. The specific problem we consider is that of gravity-capillary wave excitation on the free surface of a fluid subjected to the (vertical) forcing function

$`F(t)`$ $`={\displaystyle \frac{1}{2}}(f_me^{im\omega t}+f_ne^{in\omega t}+cc.)`$ (1)
$`|f_m|\mathrm{cos}(m\omega t+\varphi _m)+|f_n|\mathrm{cos}(n\omega t+\varphi _n),`$
where $`m`$ and $`n`$ are relatively prime. This system, with its wealth of readily tuneable control parameters, has been a rich source of intriguing patterns Edwards and Fauve (1994); Kudrolli et al. (1998); Arbell and Fineberg (1998, 2000, 2001). Although a variety of nonlinear interactions influence the pattern selection process, resonant triads are especially important because they arise at second order in a weakly-nonlinear expansion and lead to a strong phase coupling between the three waves involved - they have been implicated in many Faraday wave pattern studies, both experimental Arbell and Fineberg (1998, 2000, 2001) and theoretical Zhang and Viñals (1997); Silber et al. (2000). This letter uses general symmetry arguments applied to several such three-wave interactions to shed some light on the role of the control parameters ($`|f_m|,|f_n|,m\omega ,n\omega ,\varphi _m,\varphi _n`$) in the pattern formation process.

Symmetry considerations, both spatial and temporal, have already gone a long way toward elucidating the general mechanisms by which different patterns arise. For example, when a single frequency $`\omega `$ is used, a sufficiently large forcing excites standing waves (SW) with primary frequency $`\omega /2`$. After one period $`T`$ of the driving, the SW eigenmodes $`\psi _j`$ are exactly out of phase and, due to the symmetry $`tt+T,\psi _j\psi _j`$, are barred from quadratic (i.e. three-wave) interactions. The addition of a second commensurate frequency (when not a multiple of the first) breaks this particular discrete translation symmetry and replaces it with one on a longer timescale: $`tt+pT`$. If $`p`$ is even this weaker symmetry constraint permits three-wave interactions by recasting the $`\psi _j`$ as harmonic modes. Despite the success of this argument in explaining the emergence of hexagons when a second frequency is added Edwards and Fauve (1994) it fails to predict either the size of the symmetry-breaking effect or its dependence on the control parameters.

In this letter we take advantage of nearby (approximate) symmetries to make further progress. The main idea is that, for weakly-damped small-amplitude dynamics, the real physical system (damped forced SW) is intimately related to an underlying system (undamped unforced traveling waves (TW)) that is subject to more stringent symmetry requirements: invariance under arbitrary time translations $`tt+\tau `$, and time reversal $`tt`$. If the undamped but forced problem is Hamiltonian the system is still further constrained. Although the addition of forcing and damping destroys these symmetries, their influence persists. In fact, the broken symmetries can be replaced by corresponding parameter symmetries which remain intact for any damping and forcing. It is only to obtain useful scaling laws that we must restrict ourselves to small damping and forcing.

The overall strategy is illustrated in Fig. 1.

First, we express physical variables such as surface height $`h(𝒙,t)`$ in terms of the TW eigenfunctions of the undamped unforced problem:

$`h(𝒙,t)={\displaystyle \underset{j=1}{\overset{N}{}}}{\displaystyle \underset{\pm }{}}Z_j^\pm (t)e^{i(𝒌_j𝒙\pm \mathrm{\Omega }_jt)}+cc.+\mathrm{}.`$ (2)
In all cases $`N`$ is finite (we consider only periodic patterns). Evolution equations for the TW amplitudes $`Z_j^\pm `$ must respect the appropriate spatial symmetries, which depend on the planform considered, and the following parameter symmetries:

$`T_\tau :Z_j^\pm e^{\pm i\mathrm{\Omega }_j\tau }Z_j^\pm ,(f_m,f_n)(f_me^{im\tau },f_ne^{in\tau }),`$
$`\kappa :Z_j^\pm Z_j^{},(t,\gamma )(t,\gamma ),(f_m,f_n)(\overline{f}_m,\overline{f}_n).`$ (3)
Here $`\gamma =2\nu k^2/\omega `$ is a dimensionless damping parameter ($`\nu `$ denotes viscosity and $`k(\omega )`$ is a characteristic wavenumber). Next, we assume the TW equations can be expanded in powers of $`\gamma `$, $`f_m`$ and $`f_n`$ and so determine their form for small damping and forcing. Lastly, these expanded TW equations are reduced at the primary bifurcation through a center manifold reduction to yield the equations describing SW near onset. The procedure outlined above can be applied to numerous patterns and we shall look briefly at three: hexagons, two-mode superlattices Arbell and Fineberg (2000), and two-mode rhomboids Arbell and Fineberg (1998). We test the predicted dependence of SW coefficients by numerically calculating them from the Zhang-Viñals model Zhang and Viñals (1997), a quasipotential formulation of the Faraday problem appropriate for a deep layer of nearly inviscid fluid. This reduction (see Silber et al. (2000)) is done directly at the primary bifurcation to SW and does not rely on the symmetry arguments we develop here.

I. Simple hexagons. These common patterns are favored by quadratic interactions requiring harmonic eigenmodes. We therefore take the coprime integer associated with the instability ($`n`$, say) to be even, and set $`N=3`$, $`\mathrm{\Omega }_1=\mathrm{\Omega }_2=\mathrm{\Omega }_3=n\omega /2`$ in the TW expansion (2). The neutral stability curves in the $`(k,f)`$ plane ($`f^2|f_m|^2+|f_n|^2`$)

might resemble the sketch in Fig. 2b. Spatial symmetries (translation, reflection, and $`60^{}`$ rotation) in combination with Eqs. (3) lead to

$`\dot{Z}_1^+=`$ $`\upsilon Z_1^+\stackrel{~}{\mu }f_nZ_1^{}+\varpi (Z_2^+\overline{Z}_2^{}+Z_3^+\overline{Z}_3^{})Z_1^{}`$
$`+\left\{\begin{array}{cc}\stackrel{~}{\beta }f_m^{\frac{n}{2}}(\overline{Z}_2^+\overline{Z}_3^{}+\overline{Z}_2^{}\overline{Z}_3^+)+\stackrel{~}{\gamma }\overline{f}_m^{\frac{n}{2}}\overline{Z}_2^{}\overline{Z}_3^{},\hfill & m=1\hfill \\ \stackrel{~}{\alpha }f_m^{\frac{n}{2}}\overline{f}_n^{\frac{m3}{2}}\overline{Z}_2^+\overline{Z}_3^+,\hfill & m>1\hfill \end{array}\right\}`$ (6)
$`+Z_1^+{\displaystyle \underset{j,\pm }{}}\stackrel{~}{a}_j^\pm |Z_j^\pm |^2.`$ (7)
The other five equations follow from symmetry. At each order in amplitude, up to third order, the leading order terms (in $`f_m`$, $`f_n`$, $`\gamma `$) have been kept. Terms of order $`|Z|^3f`$ are neglected here (and in the examples that follow) because they produce no new qualitative effects. Note that the quadratic terms in Eqs. (7) split into two cases: $`m=1`$ and $`m>1`$. The time reversal symmetry $`\kappa `$ in (3) forces most of the coefficients to be imaginary at leading order. For example, we may write

$`\stackrel{~}{\mu }=\stackrel{~}{\mu }_r\gamma +i(\stackrel{~}{\mu }_i+\stackrel{~}{\mu }_m|f_m|^2+\stackrel{~}{\mu }_n|f_n|^2+\stackrel{~}{\mu }_\gamma \gamma ^2)+\mathrm{}.`$ (8)
Here $`\stackrel{~}{\mu }_r,\stackrel{~}{\mu }_i`$, etc. are real and, with an appropriate sign convention for the forcing term in the governing equations, we can take $`\stackrel{~}{\mu }_i>0`$. The only coefficient which does not submit to a simple transcription of Eq. (8) is $`\upsilon `$ because, having chosen the wavevectors of the expansion to lie on the critical circle (itself a function of $`\gamma `$), we must have the detuning, $`\mathrm{Im}(\upsilon )`$, vanish at $`\gamma =f=0`$.

At the bifurcation to SW, eigenvectors take the form $`Z_j^\pm =e^{\pm i\phi }A_j`$ where $`\phi =\varphi _n/2\pi /4+𝒪(\gamma )`$. A center manifold reduction yields

$`\dot{A}_1=\mu A_1+\alpha \overline{A}_2\overline{A}_3+A_1\left(a|A_1|^2+b|A_2|^2+b|A_3|^2\right),`$ (9)
with equations for $`A_2`$ and $`A_3`$ obtained by cyclic permutation. The normal form coefficients are given (to lowest order) by

$`\alpha =|f_m|^{\frac{n}{2}}\{\begin{array}{cc}(2\stackrel{~}{\beta }_i\stackrel{~}{\gamma }_i)\mathrm{sin}\mathrm{\Phi },\hfill & m=1\hfill \\ \stackrel{~}{\alpha }_i|f_n|^{\frac{m3}{2}}\mathrm{cos}\mathrm{\Phi },\hfill & m>1\hfill \end{array}\},a=C_1\gamma ,`$ (12)
$`b=C_2\gamma +{\displaystyle \frac{|f_m|^n}{\gamma }}\{\begin{array}{cc}C_3\mathrm{cos}^2\mathrm{\Phi },\hfill & m=1\hfill \\ |C_4||f_n|^{m3}\mathrm{sin}^2\mathrm{\Phi },\hfill & m>1\hfill \end{array}\}.`$ (15)
Here $`\mathrm{\Phi }=\pi /4\varphi _f/2`$ with $`\varphi _fm\varphi _nn\varphi _m`$ (this is the only linear combination of $`\varphi _m`$ and $`\varphi _n`$ which cannot be set arbitrarily just by redefining the origin in time). The $`C_j`$ are known functions of $`\upsilon _r`$, $`\stackrel{~}{\mu }_m`$, etc., independent of $`f_m`$, $`f_n`$, $`\gamma `$ (see Porter and Silber (2002)). Note that $`\alpha `$ inherits the $`f_m`$, $`f_n`$ dependence of the corresponding resonant term in Eqs. 7 and, since at the bifurcation to SW we have $`|f_n|,|f_m|\gamma `$, it follows that $`\alpha `$ scales as $`\gamma ^{n/2}`$ if $`m=1,3`$ and $`\gamma ^{(n+m3)/2}`$ otherwise. Furthermore, $`\alpha `$ has a simple harmonic dependence on the $`T_\tau `$-invariant phase $`\mathrm{\Phi }`$. Both of these predictions are borne out in Fig. 3

for several values of $`m`$:$`n`$. This figure also illustrates how the oscillations in $`\alpha `$ can lead to oscillations in the range of forcing amplitude over which hexagons are stable. Similar oscillations have been seen experimentally Edwards and Fauve (1994); Kudrolli et al. (1998). One can understand such behavior as follows: while the linear eigenmodes are phase-locked to the forcing $`f_n`$ which parametrically excites them, the nonlinear forcing from the resonant terms (which involves $`f_m`$) attempts to induce a different temporal phase. These two influences may cooperate or compete, depending on the relative phase $`\varphi _f`$.

II. Two-mode superlattices (2MS). These were observed with almost all forcing ratios by Arbell and Fineberg Arbell and Fineberg (1998, 2001) near the bi-critical point where the two modes driven by $`f_m`$ and $`f_n`$ onset simultaneously. The relevant three-wave interaction also includes a third linearly damped mode (see Fig. 4b)

with predominant oscillations at half the “difference frequency”. The 2MS states typically emerge from an underlying square or hexagonal lattice and involve multiple resonant triads Arbell and Fineberg (1998, 2001). For simplicity, we focus here on a single characteristic triad (Fig. 4a), i.e., we treat an invariant subspace of the full 2MS problem. A combination of spatial and temporal symmetries (3) again determines the form of the six TW evolution equations. In the vicinity of the bi-critical point these TW equations reduce to SW equations

$`\dot{A}_1=\lambda A_1+A_1\left(a|A_1|^2+b|A_2|^2\right),`$
$`\dot{A}_2=\mu A_2+A_2\left(c|A_1|^2+d|A_2|^2\right),`$ (16)
with coefficients of the form

$`\left(\begin{array}{c}a\\ b\\ c\\ d\end{array}\right)=\left(\begin{array}{c}C_1\\ C_2\\ C_3\\ C_4\end{array}\right)\gamma +\left(\begin{array}{c}0\\ |C_5|\stackrel{~}{\beta }_i\stackrel{~}{\kappa }_i\\ |C_5|\stackrel{~}{\alpha }_i\stackrel{~}{\kappa }_i\\ 0\end{array}\right){\displaystyle \frac{1}{\gamma }}.`$ (29)
Here the $`C_j`$ are known functions, independent of $`\gamma `$, $`f_m`$, and $`f_n`$ while $`\stackrel{~}{\alpha }_i`$, $`\stackrel{~}{\beta }_i`$, and $`\stackrel{~}{\kappa }_i`$ are the imaginary parts of the quadratic resonant coefficients in $`\dot{Z}_1^+`$, $`\dot{Z}_2^+`$, and $`\dot{Z}_3^+`$, respectively. The most important effect of Hamiltonian structure on the TW equations comes via these last three coefficients. Specifically, if at $`\gamma =0`$ there exists a Hamiltonian $``$ such that $`dZ_j^\pm /dt=i/\overline{Z}_j^\pm `$, then $`\stackrel{~}{\alpha }_i=\stackrel{~}{\beta }_i=\stackrel{~}{\kappa }_i`$. The equality here is an overstatement since the equations (and hence the coefficients) can always be rescaled. One expects simply $`\stackrel{~}{\alpha }_i\stackrel{~}{\beta }_i\stackrel{~}{\kappa }_i`$ and thus, for small damping, $`1bc`$. If, in addition, both primary bifurcations (to pure modes) within Eqs. (16) are supercritical then $`0<ad1`$. Under these conditions stable 2MS states (mixed states within Eqs. (16)) inhabit the region shown in Fig. 5a. This region agrees quite well with the experiments of Arbell and Fineberg Arbell and Fineberg (1998) despite

being based on a simplified version of the 2MS states. The indifference of Eqs. (29) to $`m`$ and $`n`$ helps explain why 2MS patterns were observed for virtually all forcing ratios Arbell and Fineberg (1998).

III. Two-mode rhomboids (2MR). These patterns are found Arbell and Fineberg (2000) near the bi-critical point but, unlike 2MS, do not rely on damped modes; see Fig. 6.

As before, spatial symmetries and Eqs. (3) determine the form of the six TW equations that reduce to SW equations at the bi-critical point:

$`\dot{A}_1`$ $`=\lambda A_1+\alpha \overline{A}_2A_3+A_1\left(a|A_1|^2+b|A_2|^2+c|A_3|^2\right),`$
$`\dot{A}_3`$ $`=\mu A_3+\beta A_1A_2+A_3\left(d|A_1|^2+d|A_2|^2+e|A_3|^2\right),`$ (30)
with resonant coefficients of the form

$`\left(\begin{array}{c}\alpha \\ \beta \end{array}\right)=\left(\begin{array}{c}\stackrel{~}{\alpha }_i\\ \stackrel{~}{\beta }_i\end{array}\right)|f_m|^{\frac{n2}{2}}|f_n|^{\frac{m1}{2}}\mathrm{cos}\mathrm{\Phi }.`$ (35)
Again $`\mathrm{\Phi }=\pi /4\varphi _f/2`$ with $`\varphi _f=m\varphi _nn\varphi _m`$. Hamiltonian structure at $`\gamma =0`$ implies $`\stackrel{~}{\alpha }_i\stackrel{~}{\beta }_i`$ and thus $`\stackrel{~}{\alpha }_i\stackrel{~}{\beta }_i>0`$, or equivalently, $`\alpha \beta <0`$ (see Chossat (2001) for proof of an analogous relation in a class of self-adjoint hydrodynamic problems). The condition $`\alpha \beta <0`$ has enormous dynamical consequences for Eqs. (30) and is associated with the presence of modulated drifting waves and heteroclinic cycles tri ; Porter and Silber (2002). We have confirmed the opposing signs of $`\alpha `$ and $`\beta `$, as well as the predicted scaling $`|\alpha |`$, $`|\beta |\gamma ^{(m+n3)/2}`$, for a wide range of forcing ratios by numerically calculating these coefficients from the Zhang-Viñals equations. The exponential decrease of $`|\alpha |`$ and $`|\beta |`$ with $`m+n`$ helps explain why 2MR have been seen in Arbell and Fineberg (2000, 2001) for $`m`$:$`n`$ = 3:2 and 5:4 but not with higher values of $`m+n`$; for $`m`$:$`n`$ = 1:2 the same three-wave resonance is observed, but as part of a superlattice-II type state Arbell and Fineberg (2001).

In conclusion, we have shown that with weak damping the “broken” symmetries of time translation, time reversal, and Hamiltonian structure impose significant constraints on the equations describing SW near onset. These include scaling laws of resonant interactions with $`f_m`$ and $`f_n`$, harmonic dependence on $`\varphi _f`$, and the dynamically significant preference for resonant coefficients of opposite sign in the 2MR problem. We have verified numerically these predictions for the Zhang-Viñals equations, and used them to interpret experimental results - they explain the oscillations seen with varying temporal phase in Edwards and Fauve (1994); Kudrolli et al. (1998) and predict the correct region of parameter space for 2MS states. We note, however, that it is not always clear whether the damping in a given experiment is “small enough” for our results to apply. This is particularly true when shallow containers are used and the damping due to boundary layer effects is important. It is unclear as well whether some procedures (such as the simple Taylor expansion in $`\gamma `$) would carry over to the full problem (Navier-Stokes equations with realistic boundary conditions) where the addition of damping constitutes a singular perturbation.

Finally, we emphasize that the ideas developed in this letter can be fruitfully applied to a variety of other patterns, and could be extended to include more general periodic forcing functions. In particular, they indicate how one might control resonant wave interactions (and hence pattern formation) through a judicious choice of the harmonic content of the forcing function. Furthermore, many aspects of our mathematical framework, developed here for parametrically excited SW patterns, should carry over to other problems in which TW naturally occur, e.g. via Hopf bifurcation. It would be interesting, for instance, to apply our framework to the problem of SW pattern control via weak temporal modulation of the control parameter Riecke et al. (1988); Dennin (2000).

###### Acknowledgements.

We thank J. Fineberg, M. Golubitsky, H. Riecke, C. Topaz, and P. Umbanhowar for helpful discussions. This work was supported by NASA grant NAG3-2364 and NSF grant DMS-9972059.