# Novel surface state in a class of incommensurate systems

## I Introduction

It is well known that a surface field can give rise to wetting phenomena and also that enhanced interactions near a surface can give rise to surface order without bulk order . Nakanishi and Fisher  have given a unified picture of wetting and surface ordering at the phenomenological (Landau-theory) level; these effects require that surface terms be added to the bulk free energy. In this article, we report an entirely new surface effect which should occur in a particular class of incommensurate systems. We find that surface states exist and are energetically favored by the mere presence of the surface, without surface terms like those considered in .

Candidate physical systems for observing these states include highly chiral cholesterics in electric or magnetic field, where a bulk undulating phase was recently predicted to occur . This phase is an undulating structure in which the amount of orientational order varies periodically in conjunction with an oscillation of the direction of the local optic axis. It is expected to occur under appropriate conditions of temperature and a strong aligning electric or magnetic field. As discussed in section III C of reference , the order parameters for the modulated state are the amplitudes of the harmonics. The free energy that results is identical to that of Landau models in which the coefficient of the gradient-squared elastic terms is negative, necessitating the inclusion of terms quadratic in second derivatives. When the coefficient of the gradient-squared term vanishes, a Lifshitz point occurs in the phase diagram . Therefore other candidates include Lifshitz-point systems such as the magnetic material MnP , and Langmuir monolayers and diblock copolymers  with modulated phases.

Our Landau model gives a bulk temperature-field phase diagram with a closed loop separating the modulated phase (favored inside) from the homogeneous phase. The surprise is that the mere existence of the surface produces a surface state which is energetically favored within a second closed loop well outside the first. Outside the second loop, the surface state exists but it is metastable (the equilibrium solution is simply the homogeneous bulk state). The order parameter in the surface state is not a small perturbation to the bulk order parameter. The width of the state has no pronounced temperature dependence; in particular, it does not diverge. In the presence of a surface field (coupling linearly to the order parameter), the surface phase may still occur but the line of surface transitions no longer forms a closed loop. ¿From the above and other evidence, our surface states are very different from the states considered in . 

This paper is organized as follows. Section II presents the effective Landau-Ginzburg model and then describes analytical and numerical results for the bulk phase diagram. Section III presents analytical and numerical results for the surface states, in the absence of a surface field. Section IV shows how the surface phase diagram is modified by a surface field. Finally section V discusses the results and their possible realization.

## II Model and bulk phase diagram

In this section we introduce the model used in the rest of the article, and we study the bulk phase diagram, especially the transition line separating the homogeneous and modulated states. The bulk free energy $`F_b`$ is the spatial integral of the density $`_b`$, which is the following functional of the scalar order parameter $`\varphi (x)`$:

$$_b[\varphi ]=h\varphi +\frac{1}{2}r\varphi ^2+\frac{1}{4}\varphi ^4\frac{1}{2}(\varphi ^{})^2+\frac{1}{2}(\varphi ^{\prime \prime })^2$$
(1)   
where $`\varphi ^{}=d\varphi /dx`$. We have scaled the order parameter, the energy and the unit of length to simplify the coefficients, and so $`h`$ and $`r`$ are the rescaled ordering field and temperature variables respectively. The corresponding Euler-Lagrange equation is

$$\varphi ^{\prime \prime \prime \prime }+\varphi ^{\prime \prime }h+r\varphi +\varphi ^3=0.$$
(2)   
Nakanishi and Fisher examined a very different model; the gradient-squared term appeared with a positive coefficient, the $`(\varphi ^{\prime \prime })^2`$ term was omitted, and surface terms were added. Their model, without the surface terms, applies to the usual Ising model with ferromagnetic interactions; it has only the disordered and homogeneous (ferromagnetically ordered) phases, and its bulk $`(r,h)`$ phase diagram consists of a first-order line at $`h=0`$ and $`r<0`$ which terminates at a critical point at $`r=0`$. The model of Equation (1), but without the $`(\varphi ^{})^2`$ term, exhibits a Lifshitz point at $`h=r=0`$ and a first-order line for $`r<0`$.

Without the bulk field $`h`$, the model (1) has a disordered phase at high temperature ($`T`$), a second-order transition at $`r=\frac{1}{4}`$ to a modulated phase, and a strong first-order transition at $`r1.2`$ to one of two degenerate homogeneous phases; the modulated phase is almost sinusoidal over its entire range, and its wavenumber is almost independent of $`T`$. In the $`(r,h)`$ plane, the modulated phase occupies a closed loop . Outside this loop, the energetically favored phase is the homogeneous phase, with order parameter $`\varphi _0`$ found from

$$h+r\varphi _0+\varphi _{0}^{}{}_{}{}^{3}=0;$$
(3)   
its free-energy density is $`_0=h\varphi _0+\frac{1}{2}r\varphi _0^2+\frac{1}{4}\varphi _0^4`$.

Figure 1 gives the bulk phase diagram, as found for the most part by numerical solution of the Euler-Lagrange equation (2) with periodic boundary conditions. The homogeneous-modulated transition is second-order near $`r=\frac{1}{4}`$, but otherwise first-order. The second-order segment and the tricritical points at its ends are found analytically in the following.

We consider a spatially modulated order parameter and expand it in harmonics. If $`q`$ is the wavenumber of the modulated structure and $`ϵ`$ is the amplitude of the leading harmonic, then the order parameter takes the form

$$\varphi (x)=\varphi _0+ϵ\mathrm{cos}(qx)+ϵ^2[\varphi _2\mathrm{cos}(2qx)+\overline{\varphi }_2]+O(ϵ^3)$$
(4)   
where $`\varphi _2`$ and $`\overline{\varphi }_2`$ are constants to be determined. Inserting this order parameter in the free energy (1) and integrating over a period, one finds the following expansion of the free energy (per unit volume):

$$_b=_0+ϵ^2_2+ϵ^4_4+O(ϵ^6)$$
(5)   
with coefficients

$$_2=\frac{1}{4}(r+3\varphi _0^2\frac{1}{4}),$$
(6)   
$`_4`$ $`=`$ $`\frac{1}{4}(r+3\varphi _0^2+2)\varphi _2^2+\frac{1}{2}(r+3\varphi _0^2)\overline{\varphi }_2^2`$ (7)   
$`+`$ $`\frac{3}{2}\varphi _0\overline{\varphi }_2+\frac{3}{4}\varphi _0\varphi _2+\frac{3}{32}.`$ (8)   
The free energy has already been minimized with respect to the wavenumber $`q`$, giving $`q=\sqrt{1/2}+O(ϵ^2)`$. The homogeneous phase is unstable to a modulated perturbation when $`_2<0`$. Provided that $`_4>0`$ then, a second-order transition occurs at

$$h=\pm \frac{2}{3\sqrt{3}}\left(\frac{1}{8}+r\right)\sqrt{\frac{1}{4}r}.$$
(9)   
When $`_4`$ is negative, the transition to the modulated phase is first-order. To find the tricritical points separating the continuous and first-order segments, we minimize $`_4`$ with respect to $`\varphi _2`$ and $`\overline{\varphi }_2`$ and then set the result equal to zero. On the line $`_2=0`$, $`_4`$ is minimized by $`\varphi _2=2\varphi _0/3`$ and $`\overline{\varphi }_2=6\varphi _0`$; the minimum value is

$$_4=\frac{3}{32}\frac{19}{4}\varphi _0^2,$$
(10)   
and so the two tricritical points are located at

$$r=29/152,h=\pm \sqrt{6/19^3}.$$
(11)   
## III Surface phase diagram

In this section we consider the surface phase diagram of the model (1) for a semi-infinite system, with no surface field. The presence of the surface generally produces states localized near the surface, and the states are energetically favored in part of the phase diagram. We studied the surface states in the region where the bulk phase is homogeneous, and examined their transitions with varying temperature and the external field. Only a cursory examination was made in the region where the bulk is modulated; in this region, we found many solutions of the Euler-Lagrange equation, so many that a detailed analysis was felt unjustified at this time. That is, surface states and surface phase transitions may exist inside the bulk modulated loop, but have not been studied. 

We consider a system occupying the half-space $`x0`$, and we assume that the order parameter depends only on $`x`$. The bulk energy $`F_b`$ is found by integrating the density of (1). In this section, we treat the surface very simply, by assuming that it merely terminates the bulk; we thus take free boundary conditions at the surface. In section IV, however, we assume that the surface also applies a local ordering field $`h_s`$; then the total energy is $`F_b+F_s`$, where

$$F_s=h_s\varphi _s$$
(12)   
and $`\varphi _s`$ is the order parameter at $`x=0`$. The general boundary conditions are then

$$\varphi _s^{}+\varphi _s^{\prime \prime \prime }h_s=0,\varphi _s^{\prime \prime }=0.$$
(13)   
We solved the Euler-Lagrange equation (2) numerically subject to the boundary conditions (13). This equation can have many solutions, depending on the bulk field $`h`$ and the temperature variable $`r`$. Figure 2 gives the surface phase diagram for $`h_s=0`$, as found from examining these solutions. The surface states are energetically favorable inside the outer loop of the figure (with the qualification noted above), and the homogeneous states outside; the surface states exist (as solutions of the Euler-Lagrange equation) outside this loop but are only metastable there. An interesting feature is that the surface orders at $`r=1`$ for $`h=0`$, but the bulk orders only at $`r=\frac{1}{4}`$. Many more surface states were found at lower temperatures, but they were always metastable.

Figure 3 shows a typical profile of the surface state in the ordered region, for a small and negative bulk field (to break the symmetry) and $`h_s=0`$. The order parameter decays to the bulk value (which is negative) far from the surface, but it is large and positive near it; the overshooting and the damped oscillations result from a complex decay constant, as shown below. Correspondingly, when the bulk field is positive, the order parameter of the surface state is negative near the wall and then decays to the positive bulk value. Thus at $`h=0`$ there is a first-order transition at which the surface state changes sign.

To provide an analytical understanding of these numerical results and also those of the next section, we present the following stability analysis of the homogeneous bulk state. The analysis is valid when the deviation of the order parameter from the bulk value is small.

The order parameter is written as $`\varphi =\varphi _0+\psi `$, where $`\varphi _0`$ is given by (3) and $`\psi `$ is the deviation. The free-energy density $`=_b_0`$ associated with $`\psi `$ is

$$=\frac{1}{2}(r+3\varphi _{0}^{}{}_{}{}^{2})\psi ^2+\varphi _0\psi ^3+\frac{1}{4}\psi ^4\frac{1}{2}(\psi ^{})^2+\frac{1}{2}(\psi ^{\prime \prime })^2.$$
(14)   
The energy is minimized by an order parameter $`\psi `$ which satisfies the Euler-Lagrange equation

$$(r+3\varphi _{0}^{}{}_{}{}^{2})\psi +3\varphi _0\psi ^2+\psi ^3+\psi ^{\prime \prime }+\psi ^{\prime \prime \prime \prime }=0.$$
(15)   
To prepare for the next section, we include also the surface free energy (12). The boundary conditions are then

$$\psi ^{}(0)+\psi ^{\prime \prime \prime }(0)h_s=0,\psi ^{\prime \prime }(0)=0.$$
(16)   
For $`h_s=0`$, the homogeneous bulk state $`\psi =0`$ is clearly a solution of Equations (15) and (16). This solution is stable over some region of the $`(r,h)`$ plane, but it becomes unstable at the transition to the bulk modulated state.

To study the surface states, we solve Equations (15) and (12) perturbatively in $`\psi `$. The expansion starts from the solution

$$\psi _1(x)=Ae^{\alpha x}+A^{}e^{\alpha ^{}x}$$
(17)   
of the linearized Equation (15). The amplitude $`A`$ and the decay constant $`\alpha `$ are both complex; the latter (with positive real part) is found from

$$\alpha ^2=\frac{1}{2}(1+i\gamma )$$
(18)   
where $`i=\sqrt{1}`$ and $`\gamma =[4(r+3\varphi _0^2)1]^{1/2}`$. The condition $`\psi _1^{\prime \prime }(0)=0`$ in (16) gives the amplitude $`A`$ in terms of $`m=\psi (0)`$ as

$$A=\frac{m}{2}\left(1\frac{i}{\gamma }\right).$$
(19)   
It is convenient to take $`m`$ as the expansion parameter.

The solution (17) gives the free energy to order $`m^2`$. In order to obtain the free energy to the required order ($`m^4`$), one must find the higher-order contributions to $`\psi `$. Let $`\psi =\psi _1+\psi _2`$, where $`\psi _2`$ is the nonlinear part of $`\psi `$. Inserting this form in Equation (15), using (17) and keeping terms to $`m^3`$, one finds

$`\psi _2(x)`$ $`=`$ $`B_1e^{2\alpha x}+\frac{1}{2}B_2e^{(\alpha +\alpha ^{})x}+C_1e^{3\alpha x}`$ (20)   
$`+`$ $`C_2e^{(2\alpha +\alpha ^{})x}+De^{\alpha x}+c.c.`$ (21)   
with $`\psi _2(0)=\psi _2^{\prime \prime }(0)=0`$ and coefficients

$`B_1`$ $`=`$ $`\left(3+5\sqrt{3}i\right)\varphi _0m^2/126,`$ (22)   
$`B_2`$ $`=`$ $`2\varphi _0m^2/3,`$ (23)   
$`C_1`$ $`=`$ $`\left(27+11\sqrt{3}i\right)m^3/13104,`$ (24)   
$`C_2`$ $`=`$ $`\left(3+2\sqrt{3}i\right)m^3/84,`$ (25)   
$`D`$ $`=`$ $`\left({\displaystyle \frac{5}{14}}{\displaystyle \frac{19}{126}}\sqrt{3}i\right)\varphi _0m^2\left({\displaystyle \frac{7}{208}}+{\displaystyle \frac{47}{4368}}\sqrt{3}i\right)m^3.`$ (26)   
On using the result $`\psi =\psi _1+\psi _2`$ in the free energy (14) and integrating over $`x`$, one finds that the free energy of the surface state (per unit area) is given by

$$F=h_sm+a_2m^2+\frac{2}{9}\varphi _0m^3+\frac{3}{56}m^4+O(m^5)$$
(27)   
where

$$a_2=\left(r+3\varphi _0^2\right)\frac{i}{2\gamma }\frac{\alpha ^3\alpha ^3}{\alpha \alpha ^{}}.$$
(28)   
The amplitude of the surface structure is determined by minimizing the free energy with respect to $`m`$ for given surface field $`h_s`$. This amounts to satisfying the first condition in Equation (16). We now use the free energy (27) to discuss the surface phase diagram in the region where $`m`$ is small.

Consider first the case $`h_s=0`$. For zero bulk field $`h`$, $`\varphi _0=0`$ and there is no surface state when $`a_2>0`$ (that is, $`\psi =0`$). Setting $`a_2=0`$, one finds a continuous transition at $`r=1`$ from the disordered bulk state $`m=0`$ to a surface state with $`m0`$; this is the second-order point at the right of Figure 2. For field $`h0`$, the bulk order parameter $`\varphi _0`$ is also non-zero and the free-energy expansion (27) has a term in $`m^3`$; this cubic term gives a first-order transition to the surface state, again as found numerically. Near the point $`(r=1,h=0)`$, $`m`$ is small and the transition line can be found approximately from the free-energy expansion (27). Away from this point, however, the full free energy must be minimized numerically; Figure 2 gives the resulting $`(r,h)`$ surface phase diagram for $`h_s=0`$.

## IV Effect of a surface field

We consider now the surface phase diagram for non-zero surface field $`h_s`$. Positive $`h_s`$, for example, tends to increase the order parameters of all states in the region near the surface. The new feature is that the Euler-Lagrange equation must now be solved numerically for what were homogeneous bulk states at $`h_s=0`$; for lack of a better term, we refer to these surface-field-modified bulk states simply as bulk states. Figures 4 and 5 give parts of typical phase diagrams for $`h_s>0`$, as found by numerical solution of Equation (2), subject to the boundary conditions (13).

Figure 4 shows the high-temperature part of the phase diagram for $`h_s=10^4`$. The surface field breaks the transitions of Figure 2 into two first-order lines at which the surface state changes discontinuously. In the region bounded by the upper line and the left vertical (where the bulk field $`h`$ is positive), the order parameter of the surface state is negative at the boundary $`x=0`$ ($`\varphi _s<0`$). The lower line ends at a second-order point. Below this point there is a first-order transition between the paramagnetic state and the surface state with $`\varphi _s>0`$, while above it the two states are indistinguishable. The free-energy expansion (27) can be used to find this point to leading order in $`h_s`$; the result is

$`a_2`$ $`=`$ $`{\displaystyle \frac{3}{2}}\left({\displaystyle \frac{3}{14}}\right)^{1/3}h_s^{2/3},`$ (29)   
$`\varphi _0`$ $`=`$ $`{\displaystyle \frac{9}{2}}\left({\displaystyle \frac{3}{14}}\right)^{2/3}h_s^{1/3},`$ (30)   
in good agreement with the numerical results.

Figure 5 shows the low-temperature part of the phase diagram for $`h_s=10^1`$. Paradoxically, a positive surface field cooperates, rather than competes, with a negative bulk field to enhance the stability of the lower surface state (and it competes with a positive bulk field for the other). These effects occur because the order parameter of the surface state changes sign (as seen in Figure 3).

## V Discussion

We have developed and analyzed a model to describe the effect of a substrate (or a free surface) on a material which has a bulk phase transition between homogeneous and modulated states. Modulated states tend to form because the free energy of the model contains a term, quadratic in first derivatives of the order parameter, which has a negative coefficient. We treated the surface first as simply terminating the bulk, and then in addition as supplying a surface field coupling linearly to the order parameter.

The important new result of our analysis is the quite unexpected existence of solutions localized at the surface, solutions which exist even if the surface field is zero. These solutions are energetically favored for temperature and field values that are outside but not too far from the closed loop within which the modulated bulk state is stable. When the surface field differs from zero, the loop breaks apart (as shown in Figures 4 and 5).

We now turn our attention to the applicability of our results to cholesteric liquid crystals in a field . It is obviously desirable to estimate the conditions of chirality, temperature, field, and surface interactions for which the surface states should be observable. To do this, we should examine the relationship between the variables of the theory and the experimental variables, by comparing the expressions for $`_2`$ and $`_4`$ in section II of this paper with the analogous expressions in section III-C of . It is reasonable however, and far simpler, to expect the loop regions to scale by the same factors; this should be true independent of the strength of surface interactions. From Figures 1 and 2, the outer (surface-state) loop extends over the range $`4.5r<1`$ while the inner loop extends over $`1.2r<\frac{1}{4}`$, about a factor of four. Accordingly, we estimate the surface-state region to be four times the size of the undulating-state region in temperature. From , the undulating state should occur for intrinsic pitches in the range of $`1260630`$ nm, at electric fields of the order of a few hundreds of kV/cm, or magnetic fields of roughly $`40`$ T; the temperature width was estimated to be a few tenths of a degree. These conditions are very difficult to achieve and account for the fact that the undulating state has not yet been observed, although some groups plan to attempt the experiments. The surface-state region is expected to be one degree wide. Techniques sensitive to birefringence near the surface, such as Brewster-angle ellipsometry , may be able to detect the surface states.

The surface states should appear in incommensurate systems where the modulated phase is driven by a negative gradient-squared term. Conditions may be favorable in magnetic Lifshitz-point materials like MnP, or in Langmuir monolayers or diblock copolymers. Other systems in which a modulated phase is driven by a negative gradient-squared term are sodium nitrite and thiourea ; related systems are quartz and berlinite, but for these the modulated phase is two-dimensional.

###### Acknowledgements.

We thank R. Seidin for helpful discussion of the bulk phase diagram and R. C. Desai for helpful comments. This research was supported by the National Science Foundation under Science and Technology Center ALCOM Grant No. DMR 89-20147, the Einstein Center for Theoretical Physics, the Inter-University High Performance Computation Center (Tel Aviv), the Natural Sciences and Engineering Research Council of Canada, and the Meyerhoff Foundation.