# CONVERGENT APPROXIMATION FOR THE 2-BODY CORRELATION FUNCTION IN AN INTERFACE

## I Introduction

Density correlations in the vicinity of equilibrium planar interfaces have been extensively studied by numerous authors . Several methods, including the density functional theory , the capillary wave model , and the eigenstate expansion of the fluctuations  were used to calculate the correlation function. Most existing approaches have to confront a problem of divergence, caused by the vanishing energy cost of rigid shifts of the interface in an infinite system without external potential. We will focus in this work on the Hamiltonian second derivative $`\frac{\delta ^2[\rho ]}{\delta \rho (z_1)\delta \rho (z_2)}|_{\rho =\rho _0}`$ eigenstate expansion method (sometimes also called “field theoretical method”, ). In the framework of this method the divergence manifests itself in the term $`\varphi _0(z_1)\varphi _0(z_2)/\lambda _0`$ where $`\varphi _0(z)`$ and $`\lambda _0`$ are the “zero” eigenstate and eigenvalue; $`\varphi _0(z)d\rho _0(z)/dz`$ where $`\rho _0(z)`$ is the equilibrium density profile. The eigenvalue $`\lambda _0`$ is zero for vanishing external localizing field, The traditional physical explanation for the divergence is the following: the density fluctuations corresponding to the interface shifts, to the first order of shift amplitude, have component only along the zero eigenstate, $`\mathrm{\Delta }\rho (z)=\rho _0(z+\mathrm{\Delta }z)\rho _0(z)=d\rho (z)/dz\mathrm{\Delta }z+𝒪(\mathrm{\Delta }z)^2`$, and free wandering of the interface as a whole results in the ambiguity in defining the density-density correlation function. In the framework of the capillary wave model () this ambiguity is overcome by renormalizing the equilibrium density profile by taking into account the free wandering mode. As a result, average width of the renormalized interface diverges for vanishing external field, and the zero-order term contribution to the density-density correlation function tends to zero. However, after such renormalization, one loses information about instantenous and local fluctuations of the interface.

In an attempt to resolve this ambiguity, we would like to focus our attention on the question of divergence of the zero eigenstate term The main motivation of our approach lies in the following.

It is true that in an infinite system without a confining external field the energy cost of rigid shifts of the planar two-phase interface is zero, $`[\rho (z_0+\mathrm{\Delta }z)]=[\rho (z_0)]`$. Yet this does not mean that the amplitude $`a_0`$ of the density fluctuation proportional to the zero eigenstate, $`\delta \rho (z)=a_0\rho _o^{}(z)`$ can grow infinitely without a free-energy penalty. Physically it follows from the fact, that although the position of the interface is undetermined, the actual values of the density near the interface cannot go significantly beyond the density of either of the bulk phases. For all the realistic Hamiltonian functionals describing stable systems, this non-divergence is controlled by a positive coefficient in front of the highest power of the density. For the Ginzburg-Landau functional

$$[\rho ]=(\{\frac{d}{dz}\rho (z)\}^2+\{1\rho ^2(z)\}^2)𝑑z$$
(1)   
the latter is $`+\rho ^4(z)`$. The divergence that appears when only the harmonic (second-order) terms of the expansion of the Hamiltonian are used is the direct consequence of neglect of all higher-order terms. Hence, to eliminate the divergence of the zero-eigenstate term in the correlation function, it is natural to try using higher-order terms of the expansion of the Hamiltonian around the equilibrium density profile (see  where the equilibrium profile was calculated using higher-order terms). It turns out that fourth-order terms are sufficient to keep the zero-eigenstate contribution finite. We propose an approximate method to consider these fourth order terms; this method is formally introduced in Section II. Concrete examples for the Ginzburg-Landau Hamiltonian for one- and three- dimensional systems are presented in Sections III and IV.

However, after eliminating the divergence of the zero-order eigenstate term, it is natural to ask, which eigenstate or combination of eigenstates of the second derivative matrix describe the macroscopic shifts of the interface $`\mathrm{\Delta }\rho (z)=\rho _0(z+\mathrm{\Delta }z)\rho _0(z)`$? The expansion coefficient of this density fluctuation along the zero eigenstate remains finite even for infinite shifts,

$$_{\mathrm{}}^+\mathrm{}\mathrm{\Delta }\rho (z)\rho _0^{}(z)𝑑z\rho _0(+\mathrm{})[\rho _0(+\mathrm{})\rho _0(\mathrm{})]$$
(2)   
for $`\mathrm{\Delta }z+\mathrm{}`$. This statement could serve as another argument for a finite average value of the amplitude of fluctuation along $`\rho _0^{}(z)`$. The same is true for all other bound (localized) eigenstates. Yet the projection of the shift $`\rho _0(z+\mathrm{\Delta }z)\rho _0(z)`$ onto low-lying continuum states diverges as $`\mathrm{\Delta }z\mathrm{}`$. For the Ginzburg-Landau Hamiltonian the mean-field equilibrium density profile is $`\rho _0(z)=\mathrm{tanh}(z)`$, and the first non-localized eigenstate of the second derivative matrix is proportional to $`(3\mathrm{tanh}(z)1)/2`$. The integral

$$_{\mathrm{}}^+\mathrm{}(\mathrm{tanh}(z+\mathrm{\Delta }z)\mathrm{tanh}(z))(3/2\mathrm{tanh}(z)1/2)𝑑z2\mathrm{\Delta }z$$
(3)   
diverges linearly for $`\mathrm{\Delta }z\mathrm{}`$. It means that since macroscopic shifts have no energy cost, the appropriate linear combination of low-lying continuum states with some of the coefficients growing proportionally to the magnitude of the shift also has no energy cost. The finiteness of the average values of all the continuum spectrum amplitudes is another artifact of second-order truncation; in particular, it is a result of the neglect of the mixing of different harmonics in the third and higher-order terms. Consequently, our approximation is convergent only because, after going to the higher-order expansion in the zero term, we stopped short of going beyond the harmonic approximation for terms containing the lowest-lying continuum states.

However, the main contribution to the correlations near the interface comes from the bound states, while continuum states are more relevant for the correlations in the bulk phases. A possible merit of our approximation is the improvement in the accuracy of density correlation calculations in the vicinity of the interstate. To compare our results to experimental data, theoretical calculations should be supplemented by a priori knowledge of the macroscopic localization of the interface.

For a three-dimensional system the situation is similar. For square-gradient energy functionals, the perturbation $`\mathrm{\Delta }\rho (x,y,z)=\rho _0(z+f(x,y))\rho _0(z)`$ of an initially flat interface has the energy cost

$$\mathrm{\Delta }F=_{\mathrm{}}^+\mathrm{}[\rho _0^{}(z)]^2𝑑z_{\mathrm{}}^+\mathrm{}_{\mathrm{}}^+\mathrm{}|f(x,y)|^2𝑑x𝑑y$$
(4)   
For long-wavelength fluctuations, $`f(x,y)\mathrm{exp}[i(k_xx+k_yy)]`$, $`|\stackrel{}{k}|1`$, the energy cost of such fluctuations vanishes as $`|k|^2`$. However, considering the expansion of the density fluctuations over the system of eigenstates (now in 3D) of the Hamiltonian second derivative matrix, $`\psi _i(\stackrel{}{r})1/L\varphi _i(z)\mathrm{exp}(ik_xx)\mathrm{exp}(ik_yy)`$, the divergent contribution comes not from the terms with localized $`\varphi _i`$, but from the bottom of the continuum of $`z`$-coordinate eigenstates. To illustrate that, in section IV we calculate the convergent contribution to the correlation function from the $`\varphi _0(z)\mathrm{exp}(ik_xx)\mathrm{exp}(ik_yy)`$ eigenstate.

## II Formalism

A density-density correlation function $`g(z_1,z_2)`$ is defined as a thermal average of a product of density fluctuations $`\mathrm{\Delta }\rho (z)=\rho (z)\rho _0(z)`$ around the equilibrium density profile $`\rho _0(z)`$:

$$g(z_1,z_2)\mathrm{\Delta }\rho (z_1)\mathrm{\Delta }\rho (z_2).$$
(5)   
For simplicity, in this section we consider a one-dimensional case, $`\rho =\rho (z)`$. Following  we express it as a functional integral over all possible density profiles,

$$g(z_1,z_2)=(1/Z)𝒟\rho \mathrm{\Delta }\rho (z_1)\mathrm{\Delta }\rho (z_2)\mathrm{exp}\{[\rho ]\}$$
(6)   
where $`[\rho ]H[\rho ]/k_bT`$ is a reduced Hamiltonian functional, and the partition function $`Z`$ serves as the normalization constant,

$$Z=𝒟\rho \mathrm{exp}\{[\rho ]\}$$
(7)   
In the mean-field approximation that we will use through this work, the equilibrium density profile $`\rho _0(z)`$ is determined as the one that minimizes the Hamiltonian,

$$\frac{\delta [\rho ]}{\delta \rho (z)}|_{\rho =\rho _0}=0.$$
(8)   
To evaluate (6), we proceed by calculating the eigenstates of the integral operator with the kernel $`\frac{\delta ^2[\rho ]}{\delta \rho (z_1)\delta \rho (z_2)}|_{\rho =\rho _0}`$,

$$\frac{\delta ^2[\rho ]}{\delta \rho (z_1)\delta \rho (z_2)}|_{\rho =\rho _0}\varphi _i(z_2)dz_2=\lambda _i\varphi _i(z_1).$$
(9)   
There is always a special eigenstate corresponding to $`\varphi _0(z)=d\rho _0(z)/dz`$ which has zero eigenvalue $`\lambda _0=0`$ since

$$\frac{\delta ^2[\rho ]}{\delta \rho (z_1)\delta \rho (z_2)}|_{\rho =\rho _0}\frac{d\rho _0(z_2)}{dz_2}dz_2=\frac{d}{dz}\frac{\delta [\rho ]}{\delta \rho (z)}|_{\rho =\rho _0}0.$$
(10)   
The Hamiltonian is usually real and contains only even powers of differential operators; it makes the integral operator in Eq. (9) Hermitian. The system of eigenstates $`\varphi _i`$ is complete and orthogonal; we also assume that it is normalized with unit weight function and all eigenfunctions $`\varphi _i`$ are made real. An arbitrary density fluctuation $`\mathrm{\Delta }\rho (z)=\rho (z)\rho _0(z)`$ can be expanded over the complete set of functions $`\{\varphi _i(z)\}`$:

$$\mathrm{\Delta }\rho (z)=\underset{i=0}{\overset{\mathrm{}}{}}a_i\varphi _i(z),a_i=\mathrm{\Delta }\rho (z)\varphi _i(z)𝑑z$$
(11)   
Using the expansion(11), the functional integral (6) can be expressed as

$$g(z_1,z_2)=\frac{1}{Z}\underset{i=0}{\overset{\mathrm{}}{}}\underset{j=0}{\overset{\mathrm{}}{}}\mathrm{}a_ia_j\varphi _i(z_1)\varphi _j(z_2)\mathrm{exp}\{[\rho _0+\underset{k=0}{\overset{\mathrm{}}{}}a_k\varphi _k]\}\underset{m=0}{\overset{\mathrm{}}{}}da_m$$
(12)   
where the normalization constant

$$Z=\mathrm{}\mathrm{exp}\{[\rho _0+\underset{k=0}{\overset{\mathrm{}}{}}a_k\varphi _k]\}\underset{m=0}{\overset{\mathrm{}}{}}da_m.$$
(13)   
We assume here that the integrals in both numerator and denominator are convergent. As we mentioned in the Introduction, it is not true for the single specific direction in the space of coefficients $`\{a_i\}`$, corresponding to the rigid macroscopic shifts of the interface. However, as a result of the approximations made below, this divergence will not affect the further calculations.

Traditionally, $`[\rho _0+_{k=0}^{\mathrm{}}a_k\varphi _k]`$ is expanded to the second order around the equilibrium density profile, the orthogonality conditions for the $`\varphi _i`$ are used, and the corresponding Gaussian integrals factorized . As a result, the familiar expression for the density-density correlation function is recovered:

$$g(z_1,z_2)=\underset{i=0}{\overset{\mathrm{}}{}}a_i^2\varphi _i(z_1)\varphi _i(z_2),$$
(14)   
where $`a_i^2=1/\lambda _i`$. As we already mentioned, the zero term diverges since $`\lambda _0=0`$.

However, as we discussed in the Introduction, from physical considerations $`a_0^2`$ must have finite value. It is indeed the case if in Eqs. (12), (13) one goes to higher than second order in the expansion of $`[\rho ]`$.

In our case, the expansion of $`[\rho ]`$ up to the fourth order in the density fluctuation around the equilibrium profile is sufficient:

$`[\rho _0+{\displaystyle \underset{k=0}{\overset{\mathrm{}}{}}}a_k\varphi _k]`$ (15)   
$`{\displaystyle \underset{k=0}{\overset{\mathrm{}}{}}}a_k{\displaystyle \frac{\delta [\rho ]}{\delta \rho (z)}}|_{\rho =\rho _0}\varphi _k(z)dz+`$ (16)   
$`{\displaystyle \frac{1}{2}}{\displaystyle \underset{k,l=0}{\overset{\mathrm{}}{}}}a_ka_l{\displaystyle \frac{\delta ^2[\rho ]}{\delta \rho (z_1)\delta \rho (z_2)}}|_{\rho =\rho _0}\varphi _k(z_1)\varphi _l(z_2){\displaystyle \underset{j=1}{\overset{2}{}}}dz_j+`$ (17)   
$`{\displaystyle \frac{1}{3!}}{\displaystyle \underset{k,l,m=0}{\overset{\mathrm{}}{}}}a_ka_la_m{\displaystyle \frac{\delta ^3[\rho ]}{\delta \rho (z_1)\delta \rho (z_2)\delta \rho (z_3)}}|_{\rho =\rho _0}\varphi _k(z_1)\varphi _l(z_2)\varphi _m(z_3){\displaystyle \underset{j=1}{\overset{3}{}}}dz_j+`$ (18)   
$`{\displaystyle \frac{1}{4!}}{\displaystyle \underset{k,l,m,n=0}{\overset{\mathrm{}}{}}}a_ka_la_ma_n{\displaystyle \frac{\delta ^4[\rho ]}{\delta \rho (z_1)\delta \rho (z_2)\delta \rho (z_3)\delta \rho (z_4)}}|_{\rho =\rho _0}\varphi _k(z_1)\varphi _l(z_2)\varphi _m(z_3)\varphi _n(z_4){\displaystyle \underset{j=1}{\overset{4}{}}}dz_j.`$ (19)   
The first order term is identically zero, the second-order terms are used in the traditional formalism, and the third and fourth-order terms are essential for our treatment. If we substitute this expansion into the expressions for the correlations function (12), (13), for non-pathological forms of the Hamiltonian functional $`[\rho ]`$, it will produce a finite value for $`a_0^2`$. However, in their complete form Eqs. (12), (13), (15) are hardly tractable. Assuming that we are far enough from a critical point, we use the following approximation to evaluate $`a_0^2`$. We assume that the second-order expansion works well enough for all $`a_i^2=1/\lambda _i`$ with $`i0`$ and drop from Eq. (15) all terms that do not contain $`a_0`$. In the remaining terms we replace all combinations of $`a_i`$, $`a_ia_j`$, $`a_ia_ja_k`$, $`\{i,j,k\}0`$ by their average values obtained with the second-order expansion:

$`a_i=0,`$ (20)   
$`a_ia_j=\delta _{ij}{\displaystyle \frac{1}{\lambda _i}},`$ (21)   
$`a_ia_ja_k=0.`$ (22)   
This approximations allow us to express $`a_0^2`$ in the form of the following integral:

$$a_0^2=\frac{x^2\mathrm{exp}\{\alpha x^4\beta x^2\gamma x\delta x^3\}𝑑x}{\mathrm{exp}\{\alpha x^4\beta x^2\gamma x\delta x^3\}𝑑x},$$
(24)   
with coefficients $`\alpha ,\beta ,\gamma `$ given by

$`\alpha ={\displaystyle \frac{1}{4!}}{\displaystyle \frac{\delta ^4[\rho ]}{\delta \rho (z_1)\delta \rho (z_2)\delta \rho (z_3)\delta \rho (z_4)}}|_{\rho =\rho _0}\varphi _0(z_1)\varphi _0(z_2)\varphi _0(z_3)\varphi _0(z_4){\displaystyle \underset{j=1}{\overset{4}{}}}dz_j,`$ (25)   
$`\beta ={\displaystyle \frac{1}{4}}{\displaystyle \underset{i=1}{\overset{\mathrm{}}{}}}{\displaystyle \frac{1}{\lambda _i}}{\displaystyle \frac{\delta ^4[\rho ]}{\delta \rho (z_1)\delta \rho (z_2)\delta \rho (z_3)\delta \rho (z_4)}}|_{\rho =\rho _0}\varphi _i(z_1)\varphi _i(z_2)\varphi _0(z_3)\varphi _0(z_4){\displaystyle \underset{j=1}{\overset{4}{}}}dz_j,`$ (26)   
$`\gamma ={\displaystyle \frac{1}{2}}{\displaystyle \underset{i=1}{\overset{\mathrm{}}{}}}{\displaystyle \frac{1}{\lambda _i}}{\displaystyle \frac{\delta ^3[\rho ]}{\delta \rho (z_1)\delta \rho (z_2)\delta \rho (z_3)}}|_{\rho =\rho _0}\varphi _i(z_1)\varphi _i(z_2)\varphi _0(z_3){\displaystyle \underset{j=1}{\overset{3}{}}}dz_j,`$ (27)   
$`\delta ={\displaystyle \frac{1}{3!}}{\displaystyle \frac{\delta ^3[\rho ]}{\delta \rho (z_1)\delta \rho (z_2)\delta \rho (z_3)}}|_{\rho =\rho _0}\varphi _0(z_1)\varphi _0(z_2)\varphi _0(z_3){\displaystyle \underset{j=1}{\overset{3}{}}}dz_j.`$ (28)   
## III Ginzburg-Landau Hamiltonian

To illustrate our approach let us a consider a simple 1D system with the Ginzburg-Landau Hamiltonian (1). The equilibrium density profile for symmetric boundary conditions $`\rho (l)=1`$, $`\rho (+l)=1`$, $`l\mathrm{}`$ is $`\rho _0(z)=\mathrm{tanh}(z)`$. The eigenvalue equation (9) takes the differential form

$$2\frac{d^2}{dz^2}\varphi _i(z)4\varphi _i(z)+12\mathrm{tanh}^2(z)\varphi _i(z)=\lambda _i\varphi _i(z),$$
(30)   
and the third and fourth-order functional derivatives of $`[\rho ]`$ are:

$$\frac{\delta ^3[\rho ]}{\delta \rho (z_1)\delta \rho (z_2)\delta \rho (z_3)}|_{\rho =\rho _0}=24\mathrm{tanh}(z_1)\delta (z_1z_2)\delta (z_2z_3)$$
(31)   
$$\frac{\delta ^4[\rho ]}{\delta \rho (z_1)\delta \rho (z_2)\delta \rho (z_3)\delta \rho (z_4)}|_{\rho =\rho _0}=24\delta (z_1z_2)\delta (z_2z_3)\delta (z_3z_4).$$
(32)   
In fact, the expansion (15) is now exact for $`[\rho ]`$ since all higher-order variational derivatives are identically equal to zero. To proceed further we need to calculate $`\alpha `$, $`\beta `$, $`\gamma `$, and $`\delta `$ as defined in Eq. (25). From parity consideration, the coefficients $`\gamma `$ and $`\delta `$ are zero.

The calculation of $`\alpha `$ is straightforward:

$$\alpha =\frac{9}{16}_{\mathrm{}}^+\mathrm{}\frac{dz}{\mathrm{cosh}^8(z)}=\frac{18}{35}.$$
(33)   
The coefficient $`\frac{9}{16}`$ appears from the normalization condition:

$$_{\mathrm{}}^+\mathrm{}\varphi _i^2(z)𝑑z=1.$$
(34)   
To evaluate $`\beta `$ we need to know the eigenstates $`\varphi _i(z)`$ of Eq. (30):

$$\beta =\frac{9}{2}\underset{i=1}{\overset{\mathrm{}}{}}_{\mathrm{}}^+\mathrm{}\frac{\varphi _i^2(z)}{\lambda _i}\frac{dz}{\mathrm{cosh}^4(z)}.$$
(35)   
The sum in Eq. (35) contains a contribution from one bound state, ($`\varphi _1(z)=\sqrt{3/2}\mathrm{sinh}(z)\mathrm{cosh}^2(z)`$, $`\lambda _1=6`$) and continuum states ($`i2`$) To evaluate the sum over the continuum, we use expressions obtained in  (Eq. (3.15 - 3.20)):

$$\frac{9}{2}\underset{i=2}{\overset{\mathrm{}}{}}_{\mathrm{}}^+\mathrm{}\frac{\varphi _i^2(z)}{\lambda _i}\frac{dz}{\mathrm{cosh}^4(z)}=\frac{9}{4}_{\mathrm{}}^+\mathrm{}\frac{dk}{2\pi }\frac{1}{(k^2+4)^2}\frac{1}{(k^2+1)}_{\mathrm{}}^+\mathrm{}\frac{\varphi _k(z)}{\mathrm{cosh}^4(z)}𝑑z$$
(36)   
where the continuum eigenstates $`\varphi _k(z)`$ are

$$\varphi _k(z)=\mathrm{exp}(ikz)[1+k^2+3ik\mathrm{tanh}(z)3\mathrm{tanh}^2(z)].$$
(37)   
The normalization of $`\varphi _k(z)`$ is taken into account in the $`k`$-dependent factor of the outer integral in (36). Both integrations in (36) are straightforward and finally we obtain for $`\beta `$

$$\beta \frac{6}{35}+0.0220.193$$
(38)   
The contribution from the continuum to the value of $`\beta `$ is $`13\%`$. We substitute these values of $`\alpha `$ and $`\beta `$ into Eq. (24), and, in the first order in $`\beta /\sqrt{\alpha }`$, obtain for $`a_0^2`$:

$$a_0^2\frac{x^2\mathrm{exp}\{\alpha z^4\}(1\beta z^2)𝑑z}{\mathrm{exp}\{\alpha z^4\}(1\beta z^2)𝑑z}=\frac{1}{\sqrt{\alpha }}\frac{\mathrm{\Gamma }^2(\frac{3}{4})\frac{\beta }{\sqrt{\alpha }}\frac{\pi \sqrt{2}}{4}}{\pi \sqrt{2}\frac{\beta }{\sqrt{\alpha }}\mathrm{\Gamma }^2(\frac{3}{4})}0.415$$
(39)   
It is interesting to note that if one ignores all cross-terms ( contribution from $`\beta `$) in Eq. (24), $`a_0^20.471`$. For the Ginzburg-Landau Hamiltonian, $`\frac{\beta }{\sqrt{\alpha }}0.27`$ plays the role of a small parameter in the approximations (20) - (25), as well as in (39). Hence there is a certain degree of numerical justification of heuristic assumptions made in (20) - (25). To obtain the final result for the density-density correlation function (14) we use the following method. When the external potential $`V(z)=cz`$, linear in the coordinate $`z`$ measured form the interface location $`z=0`$, is added to the Hamiltonian, the zero eigenvalue becomes proportional to the coefficient in front of this term: $`\lambda _0c`$. In  an expression for the correlation function $`G_c(z_1,z_2)`$ (Eq. (4.17) in ) is obtained in the presence of an external potential $`V(z)`$, with $`V(z)c\mathrm{tanh}(z)`$ when $`c0`$. It is shown that the zero eigenvalue $`\lambda _0/c1`$ for $`c0`$. Since for $`i1`$ all $`\lambda _i`$ go to constant limits when the external potential is turned off, the “truncated” correlation function $`\overline{g}`$ (without the zero eigenstate term) can be expressed as:

$$\overline{g}(z_1,z_2)\underset{i=1}{\overset{\mathrm{}}{}}\frac{\varphi _i(z_1)\varphi _i(z_2)}{\lambda _i}=\underset{c0}{lim}\frac{d}{dc}cG_c(z_1,z_2).$$
(40)   
To recover the “non-truncated” correlation function $`g(z_1,z_2)`$ we add to $`\overline{g}(z_1,z_2)`$ from (40) the correct contribution form the zero-order term,

$$g(z_1,z_2)=\overline{g}(z_1,z_2)+\frac{3}{4\mathrm{cosh}^2(z_1)\mathrm{cosh}^2(z_2)}a_0^2.$$
(41)   
with $`a_0^2`$ given by (39). Sketches of the density-density correlation function (41) are presented in Figs. 1,2. It is straightforward to demonstrate that far from the interface ($`z_1.z_21`$), the density-density correlation function (41) goes to the correct bulk phase limit,

$$g_{bulk}(z_1,z_2)=\frac{\mathrm{exp}(2|z_1z_2|)}{8}.$$
(42)   
## IV 3D Calculation

The next logical step is to generalize this approach to a more realistic 3D system. For simplicity, we consider the same Ginzburg-Landau Hamiltonian as in (1)

$$[\rho ]=(|\rho |^2+\{1\rho ^2(\stackrel{}{r})\}^2)𝑑\stackrel{}{r}$$
(43)   
The equilibrium density profile for the symmetric boundary conditions $`\rho (z=l)=1`$, $`\rho (z=+l)=1`$, $`l\mathrm{}`$ is the same as in the 1D case, $`\rho _0(z)=\mathrm{tanh}(z)`$. The three-dimensional analog of the eigenvalue equation (30) reads

$$2\mathrm{\Delta }\psi _i(\stackrel{}{r})4\psi _i(\stackrel{}{r})+12\mathrm{tanh}^2(z)\psi _i(\stackrel{}{r})=\lambda _i\psi _i(\stackrel{}{r}),$$
(44)   
Since the “potential” term in (44) depends only on $`z`$, the variables can be separated, $`\psi _i(\stackrel{}{r})=\varphi _i(z)\xi _i(x,y)`$. We assume that in the $`xy`$ plane the system is confined to a square box of size $`L`$ with periodic boundary conditions. Then the $`xy`$ components of the eigenstates of (44) are the normalized plane waves $`\xi _\stackrel{}{k}(x,y)=(1/L)\mathrm{exp}(ik_xx)\mathrm{exp}(ik_yy)`$ with $`k_{\{x,y\}}=2\pi n_{\{x,y\}}/L`$, $`n_{\{x,y\}}=0,\pm 1,\pm 2\mathrm{}`$. Expanding density variations over the complete set of functions $`\psi _{i\stackrel{}{k}}(\stackrel{}{r})`$ and taking the thermal average, we obtain for the density-density correlation function (compare to (12)):

$`g(\stackrel{}{r}_1,\stackrel{}{r}_2)={\displaystyle \frac{1}{Z}}{\displaystyle \underset{i,\stackrel{}{k}_1}{}}{\displaystyle \underset{j,\stackrel{}{k}_2}{}}{\displaystyle \mathrm{}a_{i.\stackrel{}{k}_1}a_{j\stackrel{}{k}_2}\psi _{i\stackrel{}{k}_1}^{}(\stackrel{}{r}_1)\psi _{j\stackrel{}{k}_2}(\stackrel{}{r}_2)}`$ (45)   
$`\mathrm{exp}\{[\rho _0+{\displaystyle \underset{m,\stackrel{}{k}_3}{}}a_{m\stackrel{}{k}_3}\psi _{m\stackrel{}{k}_3}]\}{\displaystyle \underset{n,\stackrel{}{k}_4}{}}da_{n\stackrel{}{k}_4}.`$ (46)   
Similarly to (13), $`Z`$ is a normalization constant:

$$Z=\mathrm{}\mathrm{exp}\{[\rho _0+\underset{m,\stackrel{}{k}_1}{}a_{m\stackrel{}{k}_1}\psi _{m\stackrel{}{k}_1}]\}\underset{n,\stackrel{}{k}_2}{}da_{n\stackrel{}{k}_2}.$$
(47)   
Here and below we use the shorthand notation: for sums, products, and subscript indexes symbol $`\stackrel{}{k}`$ means the set of $`xy`$ eigenstate indexes $`\{n_x,n_y\}`$. After expanding (45) to the second order in the density variation, an expression analogous to (14) is recovered:

$$g(\stackrel{}{r}_1,\stackrel{}{r}_2)=\underset{i,\stackrel{}{k}}{}a_{i\stackrel{}{k}}^2\psi _{i\stackrel{}{k}}^{}(\stackrel{}{r}_1)\psi _{i\stackrel{}{k}}(\stackrel{}{r}_2),$$
(48)   
with $`a_{i\stackrel{}{k}}^2=1/(\lambda _i+2k^2)`$. As in the (14), a similar problem arises for the $`\lambda _0=0`$ eigenstate: for $`L\mathrm{}`$ the sum on $`\stackrel{}{k}`$ diverges at the lower limit.

To avoid the divergence occurring in the $`\lambda _0=0`$ term, we suggest the same recipe as in the one-dimensional case: to continue the expansion of the Hamiltonian to the fourth order. For simplicity, we neglect mixing of the eigenstates with different $`\lambda _i`$ in the fourth-order term. Similarly to the 1D case, where the relative contribution of mixing is given by the ratio of coefficients $`\beta /\sqrt{\alpha }0.27`$ (33,38,39), the inclusion of this mixing here will not affect convergence but will slightly change the numerical values of the coefficients. For all $`\lambda _i0`$, the second-order result (48) is sufficient, hence we perform fourth-order expansion only for the subspace of eigenstates with $`\lambda _0=0`$. The contribution from the $`\lambda _0=0`$ eigenstate to the density-density correlation function can be expressed as:

$`g_0(\stackrel{}{r}_1,\stackrel{}{r}_2)={\displaystyle \frac{1}{Z_0}}{\displaystyle \underset{\stackrel{}{k}_1}{}}{\displaystyle \underset{\stackrel{}{k}_2}{}}{\displaystyle \mathrm{}a_{0\stackrel{}{k}_1}a_{0\stackrel{}{k}_2}\psi _{0\stackrel{}{k}_1}^{}(\stackrel{}{r}_1)\psi _{0\stackrel{}{k}_2}^{}(\stackrel{}{r}_2)}`$ (49)   
$`\mathrm{exp}\{[\rho _0+{\displaystyle \underset{\stackrel{}{k}_3}{}}a_{0\stackrel{}{k}_3}\psi _{0\stackrel{}{k}_3}]\}{\displaystyle \underset{\stackrel{}{k}_4}{}}da_{0\stackrel{}{k}_4},`$ (50)   
$`Z_0={\displaystyle \mathrm{}\mathrm{exp}\{[\rho _0+\underset{\stackrel{}{k}_1}{}a_{0\stackrel{}{k}_1}\psi _{0\stackrel{}{k}_1}]\}\underset{\stackrel{}{k}_2}{}da_{0\stackrel{}{k}_2}}.`$ (51)   
Using the orthogonality conditions for $`\xi _\stackrel{}{k}(z,y)`$ and Eq. (25) we obtain

$`g_0(\stackrel{}{r}_1,\stackrel{}{r}_2)={\displaystyle \frac{1}{Z_0}}{\displaystyle \underset{\stackrel{}{k}_1}{}}{\displaystyle \mathrm{}a_{0\stackrel{}{k}_1}^2\psi _{0\stackrel{}{k}_1}^{}(\stackrel{}{r}_1)\psi _{0\stackrel{}{k}_1}(\stackrel{}{r}_2)}`$ (52)   
$`\mathrm{exp}\{2{\displaystyle \underset{\stackrel{}{k}_2}{}}a_{0\stackrel{}{k}_2}^2k_2^2{\displaystyle \frac{\alpha }{L^2}}[{\displaystyle \underset{\stackrel{}{k}_3}{}}a_{0\stackrel{}{k}_3}^2]^2\}{\displaystyle \underset{\stackrel{}{k}_4}{}}da_{0\stackrel{}{k}_4},`$ (53)   
$`Z_0={\displaystyle \mathrm{}\mathrm{exp}\{2\underset{\stackrel{}{k}_1}{}a_{0\stackrel{}{k}_1}^2k_1^2\frac{\alpha }{L^2}[\underset{\stackrel{}{k}_2}{}a_{0\stackrel{}{k}_3}^2]^2\}\underset{\stackrel{}{k}_3}{}da_{0\stackrel{}{k}_3}},`$ (54)   
where $`\alpha `$ is defined by (33). Direct evaluation of the functional integrals in (52) is impossible; however, a simple approximation will allow us to obtain a physically reasonable expression for $`g_0(\stackrel{}{r}_1,\stackrel{}{r}_2)`$. The main contribution to the integral in (52) comes from $`a_{0\stackrel{}{k}}`$ with small $`|\stackrel{}{k}|`$, so in the first approximation it is natural to introduce an upper cutoff $`C`$ in sums on $`\stackrel{}{k}`$. In particular, we replace the infinite limits in all the sums and products on $`n_x`$ and $`n_y`$ in (52) by the finite cutoff, $`|n_{x,y}|\sqrt{C}L/2`$. It corresponds to a system-size-independent cutoff for a wavevector $`\stackrel{}{k}`$ with $`|k_{x,y}|\sqrt{C}\pi `$. We select $`C`$ in such a way that the term $`2_\stackrel{}{k}a_{0\stackrel{}{k}}^2k^2`$, quadratic in $`a_{0\stackrel{}{k}}`$, can be neglected in the exponent, which decouples the integration over $`da_{0\stackrel{}{k}}`$ from the summation on $`n_x,n_y`$. Besides neglecting the quadratic term, we remove the functions $`\psi _{0\stackrel{}{k}}(\stackrel{}{r})`$ from (52), and call the remaining expression $`A`$.

$$A\frac{{\displaystyle \underset{k_1}{\overset{N}{}}}{\displaystyle \mathrm{}a_{k_1}^2\mathrm{exp}\{\frac{\alpha }{L^2}[\underset{k_2=1}{\overset{N}{}}a_{k_2}^2]^2\}\underset{k_3}{\overset{N}{}}da_{k_3}}}{{\displaystyle \mathrm{}\mathrm{exp}\{\frac{\alpha }{L^2}[\underset{k_4=1}{\overset{N}{}}a_{k_4}^2]^2\}\underset{k_5}{\overset{N}{}}da_{k_5}}},$$
(55)   
with $`N=CL^2`$. This expression can be evaluated by using $`N`$-dimensional spherical coordinates, $`_k^Na_k^2R^2`$

$$A=\frac{{\displaystyle R^2\mathrm{exp}\{\frac{\alpha }{L^2}R^4\}R^{N1}\mathrm{\Omega }_N𝑑R}}{{\displaystyle \mathrm{exp}\{\frac{\alpha }{L^2}R^4\}R^{N1}\mathrm{\Omega }_N𝑑R}}=\frac{L}{\sqrt{\alpha }}\frac{\mathrm{\Gamma }(\frac{N+2}{4})}{\mathrm{\Gamma }(\frac{N}{4})}=\frac{L}{2}[\sqrt{\frac{N}{\alpha }}+𝒪(\frac{1}{\sqrt{N}})]$$
(56)   
Here $`\mathrm{\Omega }_N=2\pi ^{N/2}/\mathrm{\Gamma }(N/2)`$ is the area of the N-dimensional sphere. By inspection, one can identify $`A`$ as the sum of the first N terms of $`a^2`$, $`A=_{l=1}^Na^2`$. Therefore

$$a^2=\frac{A}{N}=\frac{1}{2}\sqrt{\frac{1}{\alpha C}}$$
(57)   
Now we return to Eq. (52) and replace one sum in the fourth-order term in the exponential by $`_{i=1}^Na^2`$:

$$\frac{\alpha }{L^2}[\underset{\stackrel{}{k}}{}a_{0\stackrel{}{k}}^2]^2\frac{\alpha }{L^2}[\underset{\stackrel{}{k}}{}a_{0\stackrel{}{k}}^2]Na^2=\frac{\sqrt{\alpha C}}{2}[\underset{\stackrel{}{k}}{}a_{0\stackrel{}{k}}^2]$$
(58)   
After this substitution, Eq. (52) becomes a product of Gaussian integrals and its evaluation becomes trivial:

$$g_0(\stackrel{}{r}_1,\stackrel{}{r}_2)\varphi _0(z_1)\varphi _0(z_2)\underset{\stackrel{}{k}}{}\stackrel{~}{a}_\stackrel{}{k}^2\frac{\mathrm{exp}[i(k_xx+k_yy)]}{L^2},$$
(59)   
where the “improved” average values $`\stackrel{~}{a}_\stackrel{}{k}^2`$ are given by

$$\stackrel{~}{a}_\stackrel{}{k}^2\frac{a_\stackrel{}{k}^2\mathrm{exp}[a_\stackrel{}{k}^2(2k^2+\sqrt{\alpha C}/2)]𝑑a_\stackrel{}{k}}{\mathrm{exp}[a_\stackrel{}{k}^2(2k^2+\sqrt{\alpha C}/2)]𝑑a_\stackrel{}{k}}=\frac{1}{4k^2+\sqrt{\alpha C}}$$
(60)   
Taking the limit $`L\mathrm{}`$ and replacing the summation $`_{n_x,n_y}`$ in (59) by the integration $`(L/2\pi )^2𝑑k_x𝑑k_y`$, we obtain

$$g_0(\stackrel{}{r}_1,\stackrel{}{r}_2)\varphi _0(z_1)\varphi _0(z_2)\frac{1}{(4\pi )^2}_0^{\mathrm{}}\frac{kdk}{k^2+\sqrt{\alpha C}/4}J_0(kr^{})=\varphi _0(z_1)\varphi _0(z_2)\frac{1}{(4\pi )^2}K_0[\frac{(\alpha C)^{1/4}r_{}}{2}].$$
(61)   
Here $`J_0`$ and $`K_0`$ are Bessel and Modified Hankel functions of zero order and $`r_{}\sqrt{(x_1x_2)^2+(y_1y_2)^2}`$. For large positive $`q`$ one has $`K_0(q)=\sqrt{\pi /2q}\mathrm{exp}(q)[1+𝒪(1/q)]`$. Consequently, we can identify $`(\alpha C)^{1/4}/2`$ with the previously introduced upper cutoff for the wavevector $`k`$, i.e., with $`\sqrt{C}\pi `$. It allows us to express the constant $`C`$ through the known parameters of the system, $`C=\alpha /(4\pi )^4`$. Finally, we write for the zero-eigenstate contribution to the correlation function:

$$g_0(\stackrel{}{r}_1,\stackrel{}{r}_2)\varphi _0(z_1)\varphi _0(z_2)\frac{1}{(4\pi )^2}K_0[\frac{\sqrt{\alpha }}{4\pi }\sqrt{(x_1x_2)^2+(y_1y_2)^2}].$$
(62)   
The contribution from other eigenstates, $`\stackrel{~}{g}(\stackrel{}{r}_1,\stackrel{}{r}_2)`$, is obtained by straightforward integration,

$$\stackrel{~}{g}(\stackrel{}{r}_1,\stackrel{}{r}_2)=\underset{j=1}{}\varphi _j(z_1)\varphi _j(z_2)\frac{1}{2(2\pi )^2}K_0[\sqrt{\frac{\lambda _j}{2}}\sqrt{(x_1x_2)^2+(y_1y_2)^2}]$$
(63)   
.

## V Conclusion

We show that taking into account the fourth-order terms in the expansion of the Hamiltonian in the calculation of the density-density correlation function makes the previously divergent (for $`D3`$) zero-eigenstate term convergent. We also note that the macroscopic shifts of the interfacial profile are described not by the zero and other bound eigenstates, but by the combination of low-lying continuum eigenstates of the Hamiltonian second-derivative matrix. The inclusion of the convergent zero-order term allows us to improve the accuracy of the calculation of the correlation function in the vicinity of the interface. Our approach could be relevant for the experimental results obtained in the microgravity conditions using a local analytical method, e.g., scattering with a narrow beam, focused on the interface.

## VI Acknowledgments

This work was done in the research group of Prof. B. Widom as part of a program supported by the U.S. National Science Foundation and the Cornell Center for Material Research. I thank Prof. Widom for having suggested this problem, for stimulating discussions during the course of the work, and for comments on the manuscript.