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# Spin tomography

## I Introduction

The main idea of tomography is to reconstruct the density matrix $`\varrho `$ or, equivalently, the expectation value of any observable of the system from repeated measurements on an ensemble of identical states. In this paper a “spin tomography” for reconstructing spin states is developed in the framework of generalized tomography, starting from group theory tomonew . There have been other proposals to infer the spin state altri . Our method is both easy to carry out experimentally and for the first time allows also a reconstruction of indistinguishable multiparticle spin 1/2 states, which is quite general since it encloses a vast class of experimentally accessible systems.

The best known quantum tomographic procedure is optical homodyne tomography tomogo , for the reconstruction of the density matrix $`\varrho _r`$ of the radiation field from the homodyne probability $`p(x,\varphi )`$. It is based on the following formula dlp

$`\varrho _r={\displaystyle _0^\pi }{\displaystyle \frac{d\varphi }{\pi }}{\displaystyle _{\mathrm{}}^+\mathrm{}}𝑑xp(x,\varphi )K(xx_\varphi ),`$ (1)
where $`x_\varphi `$ is the quadrature operator and $`K(x)`$ is an appropriate kernel function. We will not go into details about this formula, as we only want to stress the analogy with the spin case. In fact, consider the spin density operator $`\varrho `$, which is defined on a Hilbert space $`_s`$ of dimension $`2s+1`$. We will prove the following formula

$`\varrho ={\displaystyle \underset{m=s}{\overset{s}{}}}{\displaystyle \frac{d\stackrel{}{n}}{4\pi }p(\stackrel{}{n},m)K_s(m\stackrel{}{s}\stackrel{}{n})},`$ (2)
where the integral is performed over all directions of the versor $`\stackrel{}{n}`$, $`p(\stackrel{}{n},m)`$ is the probability of having outcome $`m`$ measuring the self-adjoint operator $`\stackrel{}{s}\stackrel{}{n}`$ ($`\stackrel{}{s}`$ being the spin operator), and $`K_s(x)`$ is a kernel function that will be defined later.

It is possible to show that both Eq. (1) and (2) follow from a single operator identity, derived using group theory. In fact, define Tomographic Group $`G`$ an unimodular group (i.e. left and right invariant measure are coincident) which has a unitary irreducible square–integrable representation $`(g)(gG)`$ on the Hilbert space $``$ of the physical system. \[A square–integrable representation is such that $`𝑑g|u|(g)|v|^2<\mathrm{}`$, where the integral is extended to all the elements $`g`$ of the group $`G`$, $`dg`$ is an invariant measure for $`G`$, and where the integral is not dependent on the choice of $`|u,|v`$ (as will be shown later)\]. The operator identity we derive (1) and (2) from, and which is valid for any tomographic group $`G`$, is the following

$`\varrho ={\displaystyle 𝑑g\text{T}r[\varrho (g)]^{}(g)},`$ (3)
valid for any trace class operator $`\varrho `$ acting on $``$. This formula, derived from general considerations in tomonew ; tomonew2  is derived also in App. A using only group theory.

The outline of the paper follows. In Sect. II, the tomography procedure to reconstruct the spin state of single particle systems is introduced and analyzed. The experimental setup is described and some demonstrative numerical simulations of the procedure are studied. In Sect. III the extension to the reconstruction of multi-particle spin states is studied. For distinguishable particles, the general reconstruction procedure is given, while, for indistinguishable particles, the cases of two and three spin 1/2 particles is analyzed in detail. In Sect. IV the orders of magnitude of possible experimental setups are discussed showing the feasibility of the proposed method. In App. A the group tomography is derived by proving the tomographic reconstruction formula (3) in the framework of group theory.

## II Single particle spin tomography

Starting from the general operator identity (3), we now specify the physical system as a single spin. In this case $`=^{\mathrm{\hspace{0.25em}2}s+1}`$, $`s`$ being the spin of the particle. For such a system, we can choose the group $`SU(2)`$ of $`2\times 2`$ unitary matrices with unit determinant as tomographic group $`G`$. In fact, $`SU(2)`$ can be parametrized through the “rotation parameters” $`(\stackrel{}{n},\psi )`$ —where $`\stackrel{}{n}=(\mathrm{cos}\phi \mathrm{sin}\vartheta ,\mathrm{sin}\phi \mathrm{sin}\vartheta ,\mathrm{cos}\vartheta )`$, $`\vartheta [0,\pi ],\phi [0,2\pi ],`$ and $`\psi [0,2\pi ]`$— and it induces a unitary irreducible representation on $`^{\mathrm{\hspace{0.25em}2}s+1}`$. The operators constituting this representation are given by

$`(\stackrel{}{n},\psi )=e^{i\stackrel{}{s}\stackrel{}{n}\psi },`$ (4)
where $`\stackrel{}{s}`$ is the particle spin operator. Haar’s invariant measure haar  for $`SU(2)`$ is, with this parametrization and with the normalization needed for the invariant measure (see App. A),

$`dg(\stackrel{}{n},\psi )={\displaystyle \frac{2s+1}{4\pi ^2}}\mathrm{sin}^2{\displaystyle \frac{\psi }{2}}\mathrm{sin}\vartheta d\psi d\vartheta d\phi .`$ (5)
As will be seen in the following, the choice of $`SU(2)`$ as tomographic group $`G`$ is not unique. It is easy to obtain the spin tomography (2) starting from Eq. (3), which now rewrites as

$`\varrho ={\displaystyle \frac{(2s+1)}{4\pi ^2}}{\displaystyle _0^{2\pi }}𝑑\psi \mathrm{sin}^2{\displaystyle \frac{\psi }{2}}{\displaystyle _0^\pi }𝑑\vartheta \mathrm{sin}\vartheta `$
$`\times {\displaystyle _0^{2\pi }}d\phi \text{T}r\left[\varrho e^{i\stackrel{}{s}\stackrel{}{n}\psi }\right]e^{i\stackrel{}{s}\stackrel{}{n}\psi }.`$ (6)
Evaluating the trace over the complete set of vectors $`|\stackrel{}{n},m`$ (which are the eigenstates of $`\stackrel{}{s}\stackrel{}{n}`$, relative to the eigenvalue $`m`$), we find Eq. (2), by defining

$`K_s(x){\displaystyle \frac{(2s+1)}{\pi }}{\displaystyle _0^{2\pi }}𝑑\psi \mathrm{sin}^2{\displaystyle \frac{\psi }{2}}e^{i\psi x},`$ (7)
and by noticing that $`\stackrel{}{n},m|\varrho |\stackrel{}{n},m=p(\stackrel{}{n},m)`$.

It should be pointed out that formula (1) for optical homodyne tomography can be proven from Eq. (3) with a very similar argument.

How do we use formula (2)? In order to measure the matrix elements $`\varrho _{il}=a_i|\varrho |a_l`$ for all $`i,l`$ ($`\{|a_i\}`$ being a basis for $`_s`$), we only need to calculate $`a_i|K_s(m\stackrel{}{s}\stackrel{}{n})|a_l`$ and to measure $`p(\stackrel{}{n},m)`$.

The most convenient choice for the basis $`\{|a_i\}`$ is the set $`\{|m\}`$ of eigenvectors of $`s_z`$ ($`m=s,\mathrm{},s`$). Thus, the calculation of the matrix elements of the kernel operator, by defining $`\lambda _{l,m}l|\stackrel{}{n},m`$, yields

$`i|K_s(m\stackrel{}{s}\stackrel{}{n})|l`$ (8)
$`={\displaystyle \frac{(2s+1)}{\pi }}{\displaystyle _0^{2\pi }}𝑑\psi \mathrm{sin}^2{\displaystyle \frac{\psi }{2}}{\displaystyle \underset{m^{}=s}{\overset{s}{}}}e^{i\psi (mm^{})}\lambda _{i,m^{}}\lambda _{l,m^{}}^{}`$
$`=(2s+1)\left(\lambda _{i,m}\lambda _{l,m}^{}{\displaystyle \frac{\lambda _{i,m+1}\lambda _{l,m+1}^{}+\lambda _{i,m1}\lambda _{l,m1}^{}}{2}}\right).`$
Observing that

$`|\stackrel{}{n},m=e^{i\vartheta \stackrel{}{s}\stackrel{}{n}_{}}|m,`$ (9)
with $`\stackrel{}{n}_{}(\mathrm{sin}\phi ,\mathrm{cos}\phi ,0)`$, the evaluation of $`\lambda _{l,m}`$ is given by

$`\lambda _{l,m}=l|e^{i\vartheta (\mathrm{sin}\phi s_x\mathrm{cos}\phi s_y)}|m=l|e^{i\phi s_z}e^{i\vartheta s_y}e^{i\phi s_z}|m`$
$`=e^{i\phi (ml)}\sqrt{(s+m)!(sm)!(s+l)!(sl)!}`$
$`\times {\displaystyle \underset{\nu }{}}{\displaystyle \frac{(1)^\nu (\mathrm{cos}\frac{\vartheta }{2})^{2s+ml2\nu }(\mathrm{sin}\frac{\vartheta }{2})^{lm+2\nu }}{(sl\nu )!(s+m\nu )!(\nu +lm)!\nu !}},`$ (10)
where the sum is performed over the values of $`\nu `$ for which the argument of the factorials is non-negative. In the last equality we used Wigner’s formula wigner .

### II.1 Experimental setup and state reconstruction procedure

We now describe the method to measure the state $`\varrho `$ of an ensemble of non-charged particles, giving the details of the experimental apparatus, depicted in Fig. 1. The beam of particles impinges onto a Fizeau filter, which selects one velocity (in the $`x`$ direction) for the particles. This is needed in order to ensure that each particle spends the same amount of time $`t`$ in the subsequent region where a magnetic field $`\stackrel{}{B}_1`$ is present. The field $`\stackrel{}{B}_1`$, which is parallel to the $`xy`$ plane, is chosen so that $`\stackrel{}{B}_1=B_1\stackrel{}{n}_{}=B_1(\mathrm{sin}\phi ,\mathrm{cos}\phi ,0)`$. In such way, its effect on the spin state $`\varrho `$ results in the unitary transformation $`U^{}\varrho U`$, with

$`U=\mathrm{exp}\left[i\gamma B(\mathrm{sin}\phi s_x\mathrm{cos}\phi s_y)t\right].`$ (11)
Equation (11) follows from the Hamiltonian $`H=\stackrel{}{\mu }\stackrel{}{B}`$, with $`\stackrel{}{\mu }\gamma \mathrm{}\stackrel{}{s}`$ ($`\stackrel{}{\mu }`$ being the intrinsic magnetic moment of the particle, and $`\gamma `$ its giromagnetic factor). Successively, the particles cross a gradient of magnetic field $`\stackrel{}{B}_2`$, whose effect is to split the beam, giving a measure of $`s_z`$ for the state $`U^{}\varrho U`$, as in a Stern–Gerlach experiment. In this way we obtain the probability $`m|U^{}\varrho U|m`$, which is equal to $`p(\stackrel{}{n},m)`$ by choosing $`B_1=\vartheta /(\gamma t)`$, and by using Eq. (9). Therefore, by controlling the field $`\stackrel{}{B}_1`$, we obtain $`p(\stackrel{}{n},m)`$ for all $`\stackrel{}{n}`$. In fact the direction of $`\stackrel{}{B}_1`$ selects $`\phi `$, while its intensity $`B_1`$ selects $`\vartheta `$. Now, in order to reconstruct the density matrix $`\varrho `$, only data analysis is needed, i.e. the insertion of the measured $`p(\stackrel{}{n},m)`$ into Eq. (2). One may object that an infinite number of measures are required. However, the calculation of the integral in (2) with Monte Carlo techniques guarantees that the reconstructed matrix elements are affected by statistical errors only, which can be made arbitrarily small by increasing the number of measures. In practice, a rather small number of data is required to obtain negligible errors, as we will show by numerically simulating the experiment.

We first simulate the case of a coherent spin state coher , i.e.

$`|\alpha _se^{\alpha s_+\alpha ^{}s_{}}|s,\alpha ,`$ (12)
where $`s_\pm s_x\pm is_y`$. Notice the similarity with the customary optical coherent state, defined as $`|\alpha e^{\alpha a^{}\alpha ^{}a}|0`$, where $`a`$ is the annihilator operator for the optical mode and $`|0`$ is the vacuum state. In Figs. 2 and 3 we show the reconstructed density matrix $`\varrho _{coh}=|\alpha _s_s\alpha |`$ resulting from a Monte Carlo simulated experiment.

As an additional example, in Figs. 4 and 5 we give the simulated reconstruction of a thermal spin state, which is the mixture defined by

$`\varrho _{th}{\displaystyle \frac{e^{ϵs_z}}{\text{T}r[e^{ϵs_z}]}},ϵ.`$ (13)
The state $`\varrho _{th}`$ describes a gas of non interacting spins in thermal equilibrium with a reservoir at a temperature $`T`$ and in the presence of a magnetic field $`B_z`$ parallel to the $`z`$-axis, i.e. $`ϵ=\gamma \mathrm{}B_z/(K_BT)`$, $`K_B`$ being the Boltzmann constant.

### II.2 Discrete spin tomography

Up to now $`SU(2)`$ has been used as tomographic group $`G`$ for the reconstruction of the spin density matrix. This choice for $`G`$ is not unique. For example, in the case of spin $`s=\frac{1}{2}`$, it is possible to use also the group defined as $`𝒢\{i\stackrel{}{\sigma },i\stackrel{}{\sigma },I,I\}`$, where $`\stackrel{}{\sigma }`$ is the vector of Pauli matrices $`\stackrel{}{\sigma }(\sigma _x,\sigma _y,\sigma _z)`$. The following irreducible unitary representation on $`^{\mathrm{\hspace{0.25em}2}}`$ exists

$`(i\sigma _\alpha )=(i\sigma _\alpha )=\sigma _\alpha ,\alpha =x,y,z`$
$`(I)=(I)=I.`$ (14)
Using this representation, from the tomographic reconstruction formula (3) we obtain

$`\varrho ={\displaystyle \underset{m=1/2}{\overset{1/2}{}}}{\displaystyle \underset{\alpha =x,y,z}{}}p(\stackrel{}{n}_\alpha ,m)m\sigma _\alpha +{\displaystyle \frac{1}{2}}.`$ (15)
Notice that, by using Eq. (15) it is sufficient to measure the spin in only three directions.

Analogously, for spin $`s=1`$ it is possible to find a finite group in alternative to $`SU(2)`$. In fact, consider the 12 element tetrahedric group composed of the $`\pm \frac{2}{3}\pi `$ rotations around the versors $`\{\stackrel{}{n}_1=\frac{1}{\sqrt{3}}(1,1,1),\stackrel{}{n}_2=\frac{1}{\sqrt{3}}(1,1,1),\stackrel{}{n}_3=\frac{1}{\sqrt{3}}(1,1,1),\stackrel{}{n}_4=\frac{1}{\sqrt{3}}(1,1,1)\}`$, of the $`\pi `$ rotations around $`\{\stackrel{}{n}_5=(1,0,0),\stackrel{}{n}_6=(0,1,0),\stackrel{}{n}_7=(0,0,1)\}`$ and of the identity. It induces a unitary irreducible representation on the space $`^{\mathrm{\hspace{0.25em}3}}`$, given by the $`3\times 3`$ rotation matrices. Hence, Eq. (2) now becomes

$`\varrho ={\displaystyle \frac{1}{4}}{\displaystyle \underset{m=1}{\overset{1}{}}}{\displaystyle \underset{j=1}{\overset{7}{}}}p(\stackrel{}{n}_j,m)𝒦_j(m\stackrel{}{s}\stackrel{}{n}_j)+{\displaystyle \frac{1}{4}}I,`$ (16)
with

$`𝒦_j(x)=\{\begin{array}{ccc}& 2\mathrm{cos}(\frac{2}{3}\pi x)& j=1,\mathrm{},4\\ & e^{i\pi x}& j=5,6,7\end{array}.`$ (17)
Notice that this procedure does not make use of a minimal set of measurements, since 14 experimental parameters must be determined in (16), whereas there are only 8 independent real parameters in the $`3\times 3`$ density matrix. On the contrary, the case of spin $`s=\frac{1}{2}`$ outlined previously does use the minimal set of measurements for such a system. In Fig. 6 a comparison between the two spin tomography procedures given by Eqs. (6) and (16) is shown through a Monte Carlo simulation. Notice that there is no significant difference in the results, showing that there is no substantial need for a procedure which involves a minimal set of measurements.

For spins $`s>1`$ an analogous procedure holds: one needs to find a finite group such that it induces an irreducible unitary representation on $`=^{\mathrm{\hspace{0.25em}2}s+1}`$.

## III Many particle spin tomography

The mathematical extension of the method to the case of a system composed of many spins is trivial, yet, it predicts the necessity of performing measurements on single components and this may not always be possible when the system is composed of indistinguishable particles. For this reason, we need to develop the theory more.

### III.1 Distinguishable spins.

As tomographic group for a system of $`N`$ spins we can simply use $`SU(2)^N`$. Up to equivalences, its irreducible representations are given by the direct product of $`N`$ operators (4) and the invariant measure is the product of $`N`$ measures (5). As a consequence of the tomography reconstruction formula (3) applied to $`SU(2)^N`$, we attain readily the following generalization of Eq. (6)

$`\varrho ={\displaystyle \underset{k=1}{\overset{N}{}}}{\displaystyle \frac{(2s_k+1)}{4\pi ^2}}{\displaystyle _0^{2\pi }}𝑑\psi _k\mathrm{sin}^2{\displaystyle \frac{\psi _k}{2}}{\displaystyle _0^\pi }𝑑\vartheta _k\mathrm{sin}\vartheta _k`$
$`\times {\displaystyle _0^{2\pi }}d\phi _k\text{T}r\left[\varrho e^{i\stackrel{}{s}_k\stackrel{}{n}_k\psi _k}\right]e^{i\stackrel{}{s}_k\stackrel{}{n}_k\psi _k},`$ (18)
where $`k`$ is the particle index. The trace term in (18) gives rise to the probability $`p(\stackrel{}{n}_1,m_1;\mathrm{};\stackrel{}{n}_N,m_M)`$ of obtaining $`m_k`$ as result for the measurement of the $`k`$th spin $`\stackrel{}{s}_k`$ in the direction $`\stackrel{}{n}_k`$. This information is accessible only in the case of fully distinguishable spins.

In Fig. 7 a simulated tomographic reconstruction of the value of $`S_z`$ ($`S_z`$ being the total spin component in the $`z`$-direction) is given for different multiparticle spin states. Notice how the number of the necessary experimental data increases exponentially with the number of spins, since the statistical error is exponential in the number of particles.

### III.2 Indistinguishable spin $`1/2`$ particles.

Suppose we were given a system of $`N`$ particles with the same spin. Such particles may be treated as identical by introducing a new dynamical variable, as in the case of the isospin. The spin density matrix (which is the partial trace over the orbital degrees of freedom of the global density matrix) is completely symmetrical, i.e.

$`P\varrho P^1=\varrho ,`$ (19)
for any particle permutation $`P`$, because of the complete symmetry of the global density matrix.

It is also possible to see that the spin density matrix is block diagonal in the representation of vectors of definite symmetry, with the subspace corresponding to each block spanned by vectors belonging to the same symmetry. In fact, given $`|\varphi `$ and $`|\psi `$ vectors of different symmetry type hamer , then $`\varphi |\psi =0`$. Hence, for any operator $`\varrho `$, satisfying (19), one has $`\varphi |\varrho |\psi =0`$, as $`\varrho |\psi `$ belongs to the same symmetry type as $`|\psi `$.

Since the square of the total spin $`S^2`$ and its $`z`$ component $`S_z`$ both commute with all permutation operators $`P`$, the common eigenvectors of $`S^2`$ and $`S_z`$ may be taken as a base for each of the diagonal blocks of the spin matrix. Let us now restrict our attention to $`s=1/2`$ spin particles. In this case, to each symmetry type there corresponds only one value of $`S`$, where $`S(S+1)`$ is the eigenvalue of $`S^2`$. In fact, given $`[\lambda _1\lambda _2]`$ the partition of $`N`$ which defines the class of permutations $`P`$ that indicate a symmetry type, we find $`S=\frac{1}{2}(\lambda _1\lambda _2)`$ messiah .

Let $`_{S,M}`$ be the space of vectors with assigned $`S`$ and $`M`$ ($`M`$ being the eigenvalue of $`S_z`$). The spin density matrix restricted to $`_{S,M}`$, which is given by $`\varrho _{S,M}`$, is again completely symmetrical, hence $`[P,\varrho _{S,M}]=0`$. Moreover, $`_{S,M}`$ is associated with an irreducible representation of the permutations group messiah . By using Schur’s lemma, we can thus conclude that $`\varrho _{S,M}I`$, $`I`$ being the identity in $`_{S,M}`$. In $`_{S,M}`$ there may be vectors of different symmetry type $`i`$, yet $`i,S,M|\varrho _{S,M}|i,S,M`$ does not depend on the index $`i`$, so that the probability for the measurement of $`S^2`$ and $`S_z`$ does not depend on the symmetry type. The same conclusion holds for the measurement of $`S^2`$ and $`\stackrel{}{S}m`$ for any versor $`\stackrel{}{m}`$. Hence, from the arbitrariness of $`\stackrel{}{m}`$, we conclude that blocks with the same $`S`$ (and different symmetry type) are coincident.

In conclusion, we have proved that in the $`\{S^2\}`$ representation $`\varrho `$ is block diagonal, that each block corresponds to a value of $`S`$ and that blocks with the same $`S`$ are equal. Remarkably, applying Eq. (2) to each block, we can reconstruct $`\varrho `$ measuring only the global quantities $`S^2`$ and $`\stackrel{}{S}\stackrel{}{n}`$. Some examples will clarify both the theory and the needed experimental setup.

In the case of two spins $`1/2`$, the spin density matrix will be of the form

$`\varrho =\left(\begin{array}{cccc}\sigma _{11}& \sigma _{12}& \sigma _{13}& 0\\ \sigma _{21}& \sigma _{22}& \sigma _{23}& 0\\ \sigma _{31}& \sigma _{32}& \sigma _{33}& 0\\ 0& 0& 0& \alpha \end{array}\right)\sigma \alpha ,`$ (24)
where the $`\sigma `$ block corresponds to the subspace spanned by the eigenstates of $`S=1`$ (which are symmetrical with respect to particles permutations), while the $`\alpha `$ block to the subspace spanned by the only eigenvector of $`S=0`$ (anti–symmetrical with respect to permutations). Applying (2) to each block one finds

$`\varrho `$ $`=`$ $`{\displaystyle \frac{\mathrm{d}\stackrel{}{n}}{4\pi }\underset{M=1}{\overset{1}{}}p(S=1,\stackrel{}{S}\stackrel{}{n}=M)K_{s=1}(M\stackrel{}{S}\stackrel{}{n})}`$ (25)
$``$ $`p(S=0).`$
According to (25), in order to measure $`\varrho `$, we only need the probability distributions $`p(S,\stackrel{}{S}\stackrel{}{n})`$, corresponding to the operators $`S^2`$ and $`\stackrel{}{S}\stackrel{}{n}`$, for all $`\stackrel{}{n}`$, which can be suitably recovered using the apparatus depicted in Fig. 8, which will be analyzed later.

Similarly, the spin density matrix of three spins $`1/2`$ is

$`\varrho =\left(\begin{array}{cccccccc}\xi _{11}& \xi _{12}& \xi _{13}& \xi _{14}& 0& 0& 0& 0\\ \xi _{21}& \xi _{22}& \xi _{23}& \xi _{24}& 0& 0& 0& 0\\ \xi _{31}& \xi _{32}& \xi _{33}& \xi _{34}& 0& 0& 0& 0\\ \xi _{41}& \xi _{42}& \xi _{43}& \xi _{44}& 0& 0& 0& 0\\ 0& 0& 0& 0& \pi _{11}^1& \pi _{12}^1& 0& 0\\ 0& 0& 0& 0& \pi _{21}^1& \pi _{22}^1& 0& 0\\ 0& 0& 0& 0& 0& 0& \pi _{11}^2& \pi _{12}^2\\ 0& 0& 0& 0& 0& 0& \pi _{21}^2& \pi _{22}^2\end{array}\right).`$ (34)
The $`\xi `$ block corresponds to $`S=3/2`$, whereas the $`\pi `$ blocks both correspond to $`S=1/2`$, and are distinguished by their different symmetry properties. The argument presented previously proves that $`\pi _{ij}^1=\pi _{ij}^2`$, for all $`i,j`$, thus we can write $`\varrho =\xi \pi \pi `$, with $`\pi \pi ^1=\pi ^2`$. Again, applying (2) to each block leads to

$`\xi `$ $`=`$ $`{\displaystyle \frac{\mathrm{d}\stackrel{}{n}}{4\pi }\underset{M=\frac{3}{2}}{\overset{\frac{3}{2}}{}}p(S=\frac{3}{2},\stackrel{}{S}\stackrel{}{n}=M)}`$ (35)
$`\times K_{s=\frac{3}{2}}(M\stackrel{}{S}\stackrel{}{n}),`$
$`\pi `$ $`=`$ $`{\displaystyle \frac{\mathrm{d}\stackrel{}{n}}{4\pi }\underset{M=\frac{1}{2}}{\overset{\frac{1}{2}}{}}\frac{1}{2}p(S=\frac{1}{2},\stackrel{}{S}\stackrel{}{n}=M)}`$ (36)
$`\times K_{s=\frac{1}{2}}(M\stackrel{}{S}\stackrel{}{n}),`$
and the problem of determining $`\varrho `$ is again reconducted to the simultaneous measurement of $`S^2`$ and $`\stackrel{}{S}\stackrel{}{n}`$.

Both in the cases presented and in the general $`n`$ spins case, the required experimental data are the distributions $`p(S,\stackrel{}{S}\stackrel{}{n})`$. The apparatus to produce such data are basically equivalent in the two cases, as evident in Figs. 8 and 9, hence we shall limit the analysis to the two spins case. Here, the Fizeau filter and the magnetic field $`\stackrel{}{B}_1=B_1\stackrel{}{n}_{}=B_1(\mathrm{sin}\phi ,\mathrm{cos}\phi ,0)`$ have the same purpose as in single particle tomography (Fig. 1).

Consider a beam of $`n`$ non–interacting systems composed of two particles with spin $`1/2`$. As the analysis can be immediately extended to a mixed case, for simplicity let us consider each system in the pure state

$`|\mathrm{\Psi }_o=\gamma ^s|0,0+\gamma _1^a|1,1+\gamma _0^a|1,0+\gamma _1^a|1,1,`$ (37)
with $`|a,b`$ standing for $`|S=a,M=b`$. The beam is split into three parts by the gradient $`\stackrel{}{B}_2`$, and the systems arrive in detector $`B`$ with a probability $`p(S=1,M=1)=|\gamma _1^a|^2`$ and in detector $`C`$ with a probability $`p(S=1,M=1)=|\gamma _1^a|^2`$. The remaining particles reach position $`A`$ with a probability

$`p_A=|\gamma ^s|^2+|\gamma _0^a|^2`$ (38)
and are left in the state

$`|\mathrm{\Psi }_A={\displaystyle \frac{1}{p_A}}\xi (\gamma ^s|0,0+\gamma _0^a|1,0).`$ (39)
As the subsequent gradient is directed along the $`y`$ axis, Eq. (39) is conveniently written using the eigenstates of $`S_y`$, i.e. $`|S,M_y`$:

$`|\mathrm{\Psi }_A={\displaystyle \frac{1}{p_A}}[\gamma ^s|0,0_y+\gamma _0^a\alpha _1|1,1_y+\gamma _0^a\alpha _0|1,0_y`$
$`+\gamma _0^a\alpha _1|1,1_y],`$ (40)
where $`\alpha _i_y1,i|1,0(i=1,0,1)`$. Hence, the probability for a system to arrive at detector $`D`$ is

$`p_S={\displaystyle \frac{1}{p_A}}\left[|\gamma ^s|^2+|\gamma _0^a|^2|\alpha _0|^2\right].`$ (41)
By measuring $`p_A`$ and $`p_S`$, the quantities $`|\gamma ^s|^2`$ and $`|\gamma _0^a|^2`$ are obtained by inverting equations (38) and (41). The coefficients $`|\gamma _0^a|^2`$, $`|\gamma ^s|^2`$, $`|\gamma _1^a|^2`$ and $`|\gamma _1^a|^2`$ are the four probabilities $`p(S,M)`$ we need for the reconstruction given by Eq. (25).

A similar argument shows that the equipment of Fig. 9 supplies $`p(S,M)`$, for all $`S,M`$, for a system constituted of three spins $`1/2`$.

## IV Feasibility

The orders of magnitude of the experimental parameters are such that the experiment is feasible with currently available technology. Only as an example, consider the following cases of spin measurements of electrons or nucleons. For the magnet which is responsible for the field $`\stackrel{}{B}_1`$ with length of the order of $`1`$ cm, we can measure the state of a beam of electrons with speed $`10^9`$ cm/sec, by using a magnetic field $`B_1=\vartheta /\gamma t`$ varying between $`0`$ and $`30`$ Gauss. On the other hand, in the nucleon case, choosing a speed of $`10^7`$ cm/sec, we need $`B_1`$ ranging between $`0`$ to $`10^2÷10^3`$ Gauss. Obviously, the parameters $`B_1`$ and $`t`$ can be adjusted over a wide range, according to the experimental situation.

## V Conclusions

We have presented a tomographic experimental procedure for the measurement of the spin density matrix. The experimental scheme is a consequence of formula (2), which was proved using group theory. Through some Monte Carlo simulations, we have shown that the reconstruction can be achieved with high precision using a limited number of measurements. The extension of the procedure to the reconstruction of states of multiple spin systems has been given, both for distinguishable spins and for indistinguishable spin 1/2 particles. Finally, we have shown that the orders of magnitude for the experimental setup are such that it can be implemented with currently available technology.

###### Acknowledgements.

This work has been sponsored by the INFM through the project PRA-2002-CLON and by the EEC through the project IST-2000-29681 (ATESIT).

## Appendix A Group derivation of Quantum Tomography

The proof of Eq. (3) is obtained from the following lemma.

Let $`A`$ be an arbitrary trace–class operator on the Hilbert space $``$ of the system and $``$ an irreducible unitary square integrable representation on $``$ of the tomographic group $`G`$. Then

$`\text{Tr}A={\displaystyle 𝑑g(g)A^{}(g)},`$ (42)
where $`dg`$ is an invariant measure for the group $`G`$, normalized as $`𝑑g|u|(g)|v|^2=1`$ which is independent on the choice of the vectors $`|u,|v`$.

Proof: By using the unitarity of $``$ and the properties of group representations, we can write for any $`hG`$

$`{\displaystyle 𝑑g(g)|uv|^{}(g)(h)}`$ (43)
$`=`$ $`{\displaystyle 𝑑g^{}(hg^{})|uv|^{}(g^{})}`$
$`=`$ $`(h){\displaystyle 𝑑g^{}(g^{})|uv|^{}(g^{})},`$
which, through Schur’s lemma, guarantees that

$`{\displaystyle 𝑑g(g)|uv|^{}(g)}=\tau _{u,v}I_{},`$ (44)
$`I_{}`$ being the identity in $``$. Consider the quantity

$`{\displaystyle 𝑑g|u|(g)|v|^2}=\tau _{v,v},`$ (45)
where $`|u`$ and $`|v`$ are arbitrary normalized vectors in $``$. From Eq. (44) it is trivial to see that $`\tau _{v,v}`$ is independent on $`|u`$. One can check that it is also independent on $`|v`$ by noticing that, given an arbitrary vector $`|a`$

$`\tau _{v,v}={\displaystyle 𝑑g(g)|vv|^{}(g)=𝑑h(h^1)|vv|^{}(h^1)}`$
$`={\displaystyle 𝑑h(h)|aa|^{}(h)}=\tau _{a,a},`$ (46)
where the group unimodularity has been used in $`dg=dh`$ with $`hg^1`$. Notice that the hypothesis of square–integrability of the representation guarantees the convergence of the integral in (45). Thus, the natural choice for the normalization of the group’s measure is to take $`\tau _{v,v}=1`$. The constant $`\tau _{u,v}`$ can be expressed in terms of $`\tau _{v,v}`$ by noticing that upon taking $`hg^1`$ one has

$`1=\tau _{v,v}={\displaystyle 𝑑gb|(g)|aa|^{}(g)|b}=`$
$`{\displaystyle 𝑑h\frac{a|(h)|uv|^{}(h)|a}{v|u}}={\displaystyle \frac{\tau _{u,v}}{v|u}}.`$ (47)
The lemma’s thesis is now easily found by using the Schmidt decomposition of $`A`$ as $`A=_i\alpha _i|u_iv_i|`$:

$`{\displaystyle 𝑑g(g)A^{}(g)}={\displaystyle \underset{i}{}}\alpha _i{\displaystyle 𝑑g(g)|u_iv_i|^{}(g)}=`$
$`{\displaystyle \underset{i}{}}\alpha _iv_i|u_i=\text{Tr}A.`$ (48)
Group Tomography Theorem. Let $`A`$ be an arbitrary trace–class operator on the Hilbert space $``$ of the system and $``$ an irreducible unitary square integrable representation on $``$ of the tomographic group $`G`$. Then

$`A={\displaystyle 𝑑g\text{Tr}[A(g)]^{}(g)}.`$ (49)
Proof: Let $`O`$ be an invertible trace-class operator, it follows that $`(g)O`$ is trace-class for any $`gG`$. Hence it is possible to obtain, by applying (42) twice

$`{\displaystyle 𝑑g\text{Tr}[A(g)]O^{}(g)}={\displaystyle 𝑑g^{}\text{Tr}[^{}(g^{})O](g^{})A}.`$ (50)
Take a basis $`\{|k\}`$ in $``$, one can obtain, using again lemma (42),

$`{\displaystyle 𝑑g\text{Tr}[^{}(g)O]i|(g)A|j}=`$
$`{\displaystyle 𝑑g\underset{k}{}k|^{}(g)O|ki|(g)A|j}=`$
$`{\displaystyle \underset{k}{}}k|O\text{Tr}\left[|ki|\right]A|j=i|OA|j.`$ (51)
From Eqs. (50) and (51) it follows immediately that $`𝑑g\text{Tr}[A(g)]O^{}(g)=OA`$, which yields the thesis (49) by multiplying to the left both members by $`O^1`$.

It is trivial to extend theorem (49) to the case of projective representations, i.e. group representations for which, given $`g_1`$, $`g_2`$, $`g_3G`$ such that $`g_1g_2=g_3`$, one has

$`(g_1)(g_2)=e^{i\zeta (g_1,g_2)}(g_3),`$ (52)
$`\zeta `$ being a phase factor depending on $`g_1`$ and $`g_2`$. Notice, moreover, that the theorem here presented is valid also for discrete and finite groups, with the sum on group elements replacing the integral. From result (49), with an appropriate choice for the tomographic group and the irreducible representation, it is possible to prove the formula for spin tomography (2) –derived in the following section– and for optical homodyne tomography (1). Notice that the unimodularity hypothesis given in the definition of tomographic group $`G`$ can be relaxed without losing most of the results we give in this paper.


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# Weak non-linear surface charging effects in electrolytic films

## I Introduction

Many situations in colloid, polymer and inter-facial science involve charged objects interacting in electrolyte solutions. In the case of two interacting membranes or soap films one encounters the electric double-layer. The mean-field theory of such experimental configurations is the Poisson-Boltzmann theory rusasc ; is  for which a surface boundary condition must be determined. For example, the surface charge or surface potential can be given, or a relation between the surface charge and surface potential may be specified. Such a relationship arises in a charge regularized model where the surface charging mechanism is derived from a microscopic description of the chemistry and geometry at the interface. Charge regularized models have the property that, owing to the thermodynamic nature of the charging mechanism, the surface charge changes as the distance between the two surfaces varies. The variation of the surface charge with the inter-surface distance will also change the effective interaction between the surfaces and consequently also the disjoining pressure. Within the film, the mean-field Poisson-Boltzmann theory is only sensitive to the electrostatic properties of the electrolyte; the chemistry and effective sizes of the ions in the system only enter into the description of the surface charging process. For example experiments sebe  shows that the disjoining pressure increases with increasing hydration radius of the counter-ions in ionic soap films. This effect can be explained by the fact that as the counter ion radius increases the capacity for it to approach the surface and screen the surface charge is reduced.

To take into account bulk surface tensions of electrolytes one must resort to a microscopic description of the physics at the interfaces. Depending on the nature of interface one may have specific adsorption due to chemical effects which can be taken into account via the law of mass action nipa1 ; cach ; stjo ; bebo ; maar  or at a more statistical mechanical level by introducing an external potential at the surface which models the chemical liaison involved spbe2 ; dese ; tapi . In addition, there are other forces which come into play which are not present in the standard Poisson-Boltzmann approach. These are effects due to fluctuations in the electromagnetic field which can be identified with van der Waals forces lif ; van ; mani . In bulk, the non-zero frequency van der Waals forces have little effect on the static ionic distributions since the relevant frequencies are too large and their contributions can be decoupled from those of zero frequency. However, it was pointed out in niya  that near interfaces the non-zero frequency van der Waals or dispersion forces can be important and depend strongly on the polarizability of the ions involved and hence are ion specific. The zero frequency van der Waals forces, which correspond to thermal fluctuations in the electrostatic field, do strongly influence ionic distributions and so do modify the surface charge.

When there are spatial variations in the dielectric constant image charges arise lali . In the field theoretic approach adopted in this paper image charges and their effects are naturally and systematically included by taking into account the fluctuations of the electrostatic field.

In section II we describe the field theory model we use to study the effects of non-linear terms on the surface charging mechanism whilst retaining the free field theory description for the bulk electrostatic fields. This corresponds to using linear Debye theory in the bulk with fugacity $`\mu `$ but with the fully interacting description of the sources for the charging mechanism of the surfaces. The model is applied to a triple layer thin film as an idealized model of the surfaces where there is a Stern layer of thickness $`h`$ from which all ions are excluded. In section III we discuss the mean-field solution to the field theory for the thin film for which the non-linear interactions at the surface determine the source terms in the mean-field equation. In section IV we give a detailed description of the effect of field fluctuations about the mean-field solution using the Schrödinger kernel approach developed in an earlier paper deho . We give predictions for the surface charge $`\sigma (L)`$ and the disjoining pressure $`P_d(L)`$ as a function of film thickness $`L`$ and show under reasonable assumptions that $`\sigma (L)0`$ as $`L0`$ and that the mean-field prediction for the large $`L`$ tail of $`P_d(L)`$ is modified by one-loop corrections, both decaying like $`\mathrm{exp}(mL)`$ for large $`L`$, where $`m`$ is the Debye mass . In section V we present a number of example graphs and discuss their salient features. In particular, it is clear that the effects of image charges, which arise naturally and systematically in our formalism, are very strong and that qualitative predictions depend sensitively on the value of $`h`$, the thickness of the Stern layer. This demonstrates that a realistic model for the structure of the surface and the Stern layer in particular is necessary for a quantitative study. We also present some conclusions in this section.

## II Model

We consider an idealized model of a thin film made with nonionic soap adapted to the experimental set up used to measure the disjoining pressure as a function of the film thickness my ; exkokh ; dese ; sebe ; caetal . The film shown Fig. (1) consists of two parallel surfaces of area $`A`$ the interior of which is filled with a monovalent electrolyte solution such as $`NaCl`$ in water with bulk dielectric constant $`ϵ`$. The exterior of the film is a dielectric medium of dielectric constant $`ϵ_0`$, for example, air. The perpendicular distance between the two surfaces is denoted by $`L+2h`$. The region of thickness $`h`$ is the Stern layer from which the largest ions in the system are excluded and $`h`$ can be taken to be the radius of the largest ion type in the system, which is here chosen to be the anion (in most physical systems it is the cation with the largest radius due to hydration). If the radius of the cation in solution is $`h^{}`$ and $`h^{}<h`$ then the cation is excluded from a region of width $`h^{}`$ from the surface but can be present in the region $`[(hh^{}),0]`$ where there are no anions, thus leading to an effective surface charge in that region. Strictly speaking, just outside the film is the surfactant layer which in general will have a different dielectric constant to that of the exterior and the aqueous interior. Here for simplicity the presence of the nonionic surfactant is neglected. A version of this model with a single surface plus bulk is commonly used to model the surface properties of electrolyte solutions onsa ; niya ; lefl ; kara . In experiments the thickness $`L`$ of the film may be varied by applying an external pressure in the cell containing the film and its bulk.

The grand partition function for this model system may be expressed as a functional integral

$$\mathrm{\Xi }=d[\varphi ]\mathrm{exp}\left(S[\varphi ]\right)$$
(1)
where

$`S[\varphi ]={\displaystyle \frac{1}{2}}{\displaystyle _{(T+L+2h)\times A}}\beta ϵ(𝐱)(\varphi )^2𝑑𝐱`$ $`+`$ $`2\mu {\displaystyle _{L\times A}}\text{cos}\left(\beta e\varphi \right)𝑑𝐱`$ (2)
$`+`$ $`\mu _+^{}{\displaystyle _{L\times A}}(\delta (z)+\delta (Lz))\mathrm{exp}\left(i\beta e\varphi \right)𝑑𝐱,`$
where $`e`$ is the electron charge, $`A`$ is the area of the film and $`\beta =1/k_BT`$. The fugacities of the anions and cations are taken to be equal and denoted by $`\mu `$ as are their densities denoted by $`\rho `$. The total length in the $`z`$ direction perpendicular to the film surfaces is $`T+L+2h`$ where $`T`$ denotes the total length external to the film. In the region $`z[h,L+h]`$ the dielectric constant, which is a function only of $`z`$, is given by $`ϵ(z)=ϵ`$ and outside the film $`ϵ(z)=ϵ_0`$.

The above field theoretical formulation can be obtained directly from Quantum Electrodynamics deho  by retaining just the electrostatic potential field in the QED Lagrangian and coupling it to the distribution of ion charges. Alternatively, it can be obtained by standard field theory techniques based on the Hubbard-Stratonovich transformation for a monovalent Coulomb gas. The formulation takes into account both the Coulomb interactions between the ions and the zero frequency van der Waals forces due to fluctuations in the electrostatic potential deho . These zero frequency van der Waals forces are particularly relevant when there are variations in the dielectric constants of the system since they naturally and systematically include the effects of image charges. This is especially the case for aqueous soap films in air where $`ϵ/ϵ_080`$. The density operators for the cations and anions can be shown to be

$$\rho _\pm (𝐱)=\mu \mathrm{exp}\left(\pm ie\beta \varphi (𝐱)\right)$$
(3)
The last term in Eq. (2) represents a highly localized affinity for the cations to be at the surfaces $`z=0`$ and $`z=L`$ of the film, and is responsible for the generation of a surface charge. There are various mechanisms leading to affinities for ionic species at interfaces, ranging from chemical affinity to steric and entropic effects. Here this term arises in the following approximation. Since there can be cations in the region $`[(hh^{}),0]`$ and the corresponding region $`[L,L+(hh^{})]`$ there is, in addition to the first two terms of the action Eq. (2), a surface term

$$\mathrm{\Sigma }=\mu _{[(hh^{}),0]\times A}\mathrm{exp}\left(i\beta e\varphi \right)𝑑𝐱+\mu _{[L,L+(hh^{})]\times A}\mathrm{exp}\left(i\beta e\varphi \right)𝑑𝐱.$$
(4)
This is the integral of the density operator given by Eq. (3) for the cations over the regions $`[(hh^{}),0]`$ and $`[L,L+(hh^{})]`$. These are the regions in the Stern layers which may be occupied by the cations but from which the anions are excluded. If $`hh^{}l_D`$, where $`l_D`$ is the Debye length which characterizes the scale of the electrostatic interactions, then we can approximate $`\mathrm{\Sigma }`$ by

$$\mathrm{\Sigma }=\mu (hh^{})_{L\times A}\delta (z)\mathrm{exp}\left(i\beta e\varphi \right)𝑑𝐱+\mu (hh^{})_{L\times A}\delta (zL)\mathrm{exp}\left(i\beta e\varphi \right)𝑑𝐱$$
(5)
Comparing with the formula Eq. (2) we see that $`\mu _+^{}=\mu (hh^{})`$. In general actions of the type Eq. (2) can be used to describe various surface charging mechanisms with the proviso that the region where the surface charge is localized has a width much smaller than the Debye length, $`l_D`$. Whilst this description acts as a motivation for the model it is clear that in general there will in general be specific adsorption for the different species near the air water interface. To model a specific adsorption for the cations in the surface region $`[(hh^{}),0]`$ we take a surface cation fugacity $`\mu _s`$ in this region which is greater than the bulk cation fugacity $`\mu `$. On shrinking the surface region to zero one would then have $`\mu _+^{}=\mu _s(hh^{})`$. There is some evidence for specific absorption of certain ionic species at seemingly chemically neutral interfaces; the famous and controversial Jones-Ray dip jreff  in the surface tension of weak electrolyte solutions (with interfaces with air) can be explained by invoking a specific adsorption of anions at the interface dole , although the basic surface exclusion model introduced in onsa  and used here cannot explain negative excess surface tensions. Recent experimental evidence points towards a specific adsorption of hydroxide ions at air/water and oil/water interfaces kara . In what follows we treat $`\mu _+^{}`$ as an independent variable to account for the more complex charging mechanisms which can occur at the interface.

It is important to note that the fugacities $`\mu `$ and $`\mu ^{}`$ are determined by the values of the physical bulk density $`\rho `$ and surface density for a single planar surface $`\rho _+^{}`$. We then have

$$\rho =\mu \text{cos}\beta e\varphi ,\rho _+^{}=\mu _+^{}\mathrm{exp}(i\beta e\varphi ),$$

where the brackets stand for averaging over the bulk partition function. In mean-field theory this implies $`\rho =\mu ,\rho _+^{}=\mu _+^{}`$ but this is not true in general and the relationship must be calculated taking field interactions into account.

In deho  the field theory with the action of Eq. (2) was analyzed in the weak-coupling or Debye-Hückel limit which is a Gaussian approximation where the action is expanded to second order in the field $`\varphi `$. This amounts to the assumption that the mean-field densities of cations and anions throughout the film are small enough so that $`8\pi \rho (z)l_B^3<1`$, where $`l_B`$ is the Bjerrum length $`l_B=e^2\beta /4\pi ϵ`$. Another approach is to solve the full non-linear mean-field equations and then calculate the one loop correction which gives the effect of field fluctuations about this mean-field solution atmini2 ; po . In atmini2  the resulting mean-field solution in the case of fixed surface charge was ingeniously expressed in terms of special functions which allowed an analytic calculation of the one loop correction. In our case, however, the fact that the surface charge must be computed self consistently leads to additional complications and we take a different approach. We assume that the Gaussian approximation is valid inside the film but not at the surface where, because of the increased charge density, the electrostatic interactions will be stronger and we retain the full non-linear surface operators. The resulting theory can be analyzed as before deho  but with an effective $`L`$dependent surface source for the field. The theory is accurate to the same order in perturbation theory as before but, in addition, now includes non-perturbative surface effects. The corresponding Debye-Hückel action with non-linear surface terms is

$`S^{}`$ $`[\varphi ]={\displaystyle \frac{1}{2}}{\displaystyle _{(T+L+2h)\times A}}\beta ϵ(z)(\varphi )^2𝑑𝐱{\displaystyle \frac{1}{2}}{\displaystyle _{L\times A}}\beta ϵm^2\varphi ^2𝑑𝐱`$
$`+`$ $`\mu _+^{}{\displaystyle _{L\times A}}(\delta (z)+\delta (Lz))\mathrm{exp}\left(i\beta e\varphi \right)𝑑𝐱+2\mu AL,`$ (6)
where $`m=\sqrt{8\pi \rho l_B}1/l_D`$ is the bulk Debye mass, $`l_D`$ is the Debye length and $`l_B`$ is the Bjerrum length defined above. The weak coupling limit corresponds to $`ml_B<1`$, and the Gaussian approximation will be valid throughout the film so long as the local or effective mean-field Debye mass $`m(z)=\sqrt{8\pi \rho (z)l_B}`$ does not become so large that this weak coupling condition is violated. This condition is $`8\pi \rho (z)l_B^3<1`$ as stated earlier. We note that since $`\rho (z)>\rho _{bulk}`$ this necessarily requires that $`8\pi \rho _{bulk}l_B^3<1`$.

Proceeding with the approximation scheme described above we have the expression

$$\mathrm{\Xi }d[\varphi ]\mathrm{exp}\left(S^{}[\varphi ]\right)$$
(7)
for the grand partition function. The mean-field Poisson-Boltzmann equation is obtained from the saddle point of the action $`S^{}`$:

$$\frac{\delta }{\delta \varphi (𝐱)}S^{}|_{\varphi _c}=0$$
(8)
with $`\mu _+^{}`$ replaced by $`\rho _+^{}`$. This is the correct procedure since perturbative corrections due to the interactions of field fluctuations about this mean-field, or tree level, solution will then relate $`\rho _+^{}`$ and $`\mu _+^{}`$ self-consistently order by order. In principle, the same approach applies to the bulk quantities $`\rho `$ and $`\mu `$ but since we are limiting the current analysis to a Gaussian theory in the bulk, the distinction need not be made at this stage.

Taking into account the Gaussian fluctuations about the mean-field solution gives the perturbative correction to one-loop for which we have

$$\mathrm{\Xi }\mathrm{exp}\left(S^{}[\varphi _c]\right)d[\varphi ^{}]\mathrm{exp}\left(\frac{1}{2}𝑑𝐱𝑑𝐲\frac{\delta ^2S^{}}{\delta \varphi (𝐱)\delta \varphi (𝐲)}|_{\varphi _c}\varphi ^{}(𝐱)\varphi ^{}(𝐲)\right),$$
(9)
with, again, $`\mu _+^{}`$ replaced by $`\rho _+^{}`$. All other terms are treated as interactions to be analyzed by perturbation theory.

The grand-potential per unit area of film $`J`$ can be separated into a mean-field contribution plus the zero frequency van der Waals contribution coming from the fluctuations. We write

$$J=J^{MF}+J^{vdW}$$
(10)
where

$$J^{MF}=\frac{1}{A\beta }S[\varphi _c]$$
(11)
and

$$J^{vdW}=\frac{1}{2A\beta }\mathrm{Tr}\mathrm{ln}\left(\frac{\delta ^2S^{}}{\delta \varphi (𝐱)\delta \varphi (𝐲)}|_{\varphi _c}\right)$$
(12)
## III Mean-Field Theory

The mean-field equation is obtained as usual by looking for an imaginary solution to Eq. (8) $`\varphi _c=i\psi `$ where $`\psi `$ is real and corresponds to the mean-field electrostatic potential deho . The resulting equation for $`\psi `$ is

$$\beta ϵ\psi m^2\beta ϵ\psi +\rho _+^{}\beta e(\delta (z)+\delta (Lz))\mathrm{exp}\left(\beta e\psi \right)=0,$$
(13)
within the film and outside the film one has

$$\beta ϵ_0\psi =0.$$
(14)
This mean-field equation has the form of a standard linearized Poisson-Boltzmann equation but with non-linear boundary terms with $`\mu _+^{}`$ is replaced by its mean-field approximation $`\rho _+^{}`$ as explained in the previous section.

The solution for $`\psi `$ is by symmetry only dependent on $`z`$ and symmetric about the mid-plane of the film at $`z=L/2`$ and so we choose the solution $`\psi (z)=C(L)\text{cosh}\left(m(z\frac{L}{2})\right)`$ inside the film. Outside the film Eq. (14) gives that $`d\psi /dz=0`$, which is the condition of electro-neutrality of the mean-field solution within the film. Integrating the mean-field equation between $`z=0^{}`$ and $`z=0^+`$, and using the condition of electro-neutrality, one finds

$$ϵ\frac{d\psi }{dz}|_{z=0^+}=e\rho _+^{}\mathrm{exp}\left(\beta e\psi (0)\right)$$
(15)
Defining $`D(L)=C(L)\beta e\text{cosh}(mL/2)`$ gives the non-linear self consistent equation determining $`D`$ to be

$$D(L)=\alpha \mathrm{coth}(\frac{mL}{2})\mathrm{exp}(D(L))$$
(16)
where $`\alpha =m\rho _+^{}/2\rho `$ is dimensionless. In the Stern layer model $`\alpha =m(hh^{})/2=(hh^{})/2l_D`$. As stated in Section II it is when $`l_D(hh^{})`$ that the formulation in terms of a surface charge is valid. In the study of this particular model one has that $`\alpha 1`$, which also implies small surface charges compatible with the use of the quadratic approximation within the film. Then Eq. (16) may be formally solved as a power series in $`\alpha \mathrm{coth}(\frac{mL}{2})`$ using standard series inversion techniques from complex analysis. We find that

$$D(L)=\alpha \mathrm{coth}\left(\frac{mL}{2}\right)\underset{n=0}{\overset{\mathrm{}}{}}(1)^n\left(\alpha \mathrm{coth}\left(\frac{mL}{2}\right)\right)^n\frac{(n+1)^{n1}}{n!}$$
(17)
We note that in general surface charge regulated models bebo , even if there is an exact solution to the Poisson-Boltzmann equation (or its linearized form) in the bulk, one must determine the surface potential via a transcendental equation relating the surface charge to the surface potential which in general may be solved numerically by iteration nipa1  or by linearizing the boundary equation cach . Fortunately in the case studied here we have an explicit series solution to the boundary equation. The disjoining pressure of a film $`P_d(L)`$ is the difference between the film and bulk pressures. In the grand canonical ensemble

$$P_d(L)=P(L)P_{\mathrm{bulk}}=\frac{J(L)}{L}+\underset{L\mathrm{}}{lim}J(L)/L$$
(18)
where $`J`$ is the film grand potential per unit area. We can decompose the disjoining pressure into a contribution coming from the mean-field solution and a contribution coming from the field fluctuations which corresponds to the zero frequency van der Waals interaction

$`P_d^{MF}(L)`$ $`=`$ $`{\displaystyle \frac{J^{MF}(L)}{L}}+\underset{L\mathrm{}}{lim}J^{MF}(L)/L`$ (19)
$`P_d^{vdW}(L)`$ $`=`$ $`{\displaystyle \frac{J^{vdW}(L)}{L}}+\underset{L\mathrm{}}{lim}J^{vdW}(L)/L`$ (20)
After some straightforward but laborious algebra one finds that

$$P_d^{MF}(L)=\rho k_BT\frac{D^2(L)}{\text{cosh}^2\left(\frac{mL}{2}\right)}$$
(21)
The mean-field value of the density within the film is given by

$$\rho _{MF}(𝐱)=2\rho \text{cosh}\left(e\beta \psi (𝐱)\right),$$
(22)
and in the linearized theory within the film this becomes

$$\rho _{MF}(𝐱)=2\rho +\rho e^2\beta ^2\psi (𝐱)^2.$$
(23)
At the mid-plane $`z=L/2`$ of the film one has

$$\rho _{MF}(z=\frac{L}{2}))\rho _{\mathrm{bulk}}=\rho \frac{D^2(L)}{\text{cosh}^2(\frac{mL}{2})}.$$
(24)
The mid-plane pressure formula rusasc ; is  for Poisson-Boltzmann theories with fixed surface charges or potentials, relates the disjoining pressure to the mid-plane mean-field density by

$$P_d^{MF}=k_BT[\rho _{MF}(z=\frac{L}{2})\rho _{\mathrm{bulk}}].$$
(25)
In fact, in theories of the type considered here with potentials at or near the film surface, one can show quite generally that the mid-plane formula holds generically as long as the external potential is zero in a finite interval containing the mid-plane $`z=L/2`$. One can see directly, comparing Eq. (21) and Eq. (25) with the linearized approximation Eq. (24), that the mid-plane formula is respected here.

It is useful for what follows to work with the running variable $`\alpha ^{}(L)=D(L)\mathrm{tanh}\left(\frac{mL}{2}\right)`$. The mean-field surface charge $`\sigma _{MF}(L)`$ may be written in terms of $`\alpha ^{}(L)`$

$$\sigma _{MF}(L)=\frac{2\rho e\alpha ^{}(L)}{m}$$
(26)
From Eq. (17) we have

$$\alpha ^{}(L)=\alpha \underset{n=0}{\overset{\mathrm{}}{}}(1)^n\left(\alpha \mathrm{coth}\left(\frac{mL}{2}\right)\right)^n\frac{(n+1)^{n1}}{n!}$$
(27)
As $`L\mathrm{}`$, $`\alpha ^{}`$ takes its bulk surface value $`\alpha ^{}=lim_L\mathrm{}\alpha ^{}(L)`$. As mentioned previously we are using a Gaussian field theory inside the film and so the mechanism generating the surface charge cannot be taken to be too strong, implying that $`\alpha 1`$ which gives $`\alpha ^{}\alpha `$. As $`L`$ decreases $`\alpha ^{}(L)`$ decreases. However, since the expansion in Eq. (27) is in $`\alpha \mathrm{coth}(mL/2)`$, the non-linear terms in this series must be taken into account when varying $`L`$. Indeed, for small $`L`$ one can show that $`\alpha ^{}(L)mL\mathrm{ln}(L)/2`$, which tends to zero as $`L`$ tends to zero.

The mean-field disjoining pressure in terms of $`\alpha ^{}(L)`$ is

$$P_{MF}=\rho k_BT\frac{\alpha _{}^{}{}_{}{}^{2}(L)}{\mathrm{sinh}^2(\frac{mL}{2})},$$
(28)
which, in terms of the mean-field surface charge reads

$$P_{MF}=\frac{\sigma _{MF}^2(L)}{2ϵ\mathrm{sinh}^2(\frac{mL}{2})}.$$
(29)
For the linearized Poisson-Boltzmann equation with constant surface charge $`\sigma _c`$ one finds that greg ; maar

$$P_{MF}=\frac{\sigma _c^2}{2ϵ\mathrm{sinh}^2(\frac{mL}{2})}.$$
(30)
Hence, at the mean-field level, fitting the disjoining pressure at each value of $`L`$ with an $`L`$ dependent $`\sigma _c`$ will reproduce the behavior of $`\sigma _{MF}(L)`$ in the current theory. This result is also true for full non-linear mean-field theory and is not dependent on the quadratic field approximation in the bulk used here.

## IV Fluctuation Effects

Evaluating the fluctuations about our mean-field solution yields

$`{\displaystyle \frac{1}{2}}{\displaystyle 𝑑𝐱𝑑𝐲\frac{\delta ^2S_{DH}}{\delta \varphi ^{}(𝐱)\delta \varphi ^{}(𝐲)}}|_{\varphi _c}\varphi ^{}(𝐱)\varphi ^{}(𝐲)`$ $`=`$ $`{\displaystyle \frac{1}{2}}{\displaystyle _{(T+L)\times A}}\beta ϵ(z)(\varphi ^{})^2𝑑𝐱{\displaystyle \frac{1}{2}}{\displaystyle _{L\times A}}\beta ϵm^2\varphi _{}^{}{}_{}{}^{2}𝑑𝐱`$ (31)
$`{\displaystyle \frac{1}{2}}\beta ϵm\alpha ^{}(L){\displaystyle _{L\times A}}(\delta (z)+\delta (Lz))\varphi _{}^{}{}_{}{}^{2}𝑑𝐱,`$
where

$$\alpha ^{}(L)=D(L)\mathrm{tanh}\left(\frac{mL}{2}\right)=\frac{m\rho +^{}\mathrm{exp}\left(\beta e\psi (0)\right)}{2\rho }.$$
(32)
The main difference in Eq. (33) from the pure Gaussian theory of deho  is that the surface term $`\alpha ^{}(L)`$ is now a function of the film thickness, whereas in the pure Gaussian theory it is a constant. The fluctuation term Eq. (31) may be evaluated using functional techniques mani ; atmini1 ; atmini2 ; kago ; netz2  as it is a functional determinant, or by path integral techniques deho . Using the results of deho  one finds that the terms depending explicitly on $`\alpha ^{}`$ and $`L`$ that will contribute to the disjoining pressure and the surface charge are

$`\beta J^{vdW}(L,\alpha ^{})`$ $`=`$ $`\beta J_{\mathrm{bulk}}^{vdW}L+{\displaystyle \frac{m^2}{2\pi }}{\displaystyle 𝑑kk\mathrm{ln}\left(B(km)k+\alpha ^{}(L)+\sqrt{k^2+1}\right)}`$ (33)
$`+`$ $`{\displaystyle \frac{m^2}{4\pi }}{\displaystyle 𝑑kk\mathrm{ln}\left(1\left(\frac{B(km)k+\alpha ^{}(L)\sqrt{k^2+1}}{B(km)k+\alpha ^{}(L)+\sqrt{k^2+1}}\right)^2\mathrm{exp}(2Lm\sqrt{k^2+1})\right)},`$
where

$$B(p)=\frac{1+\mathrm{\Delta }\mathrm{exp}(2ph)}{1\mathrm{\Delta }\mathrm{exp}(2ph)},$$
(34)
with $`\mathrm{\Delta }=(ϵ_0ϵ)/((ϵ_0+ϵ)`$. The term $`\beta J_{\mathrm{bulk}}^{vdW}`$ in Eq. (33) is the van der Waals contribution to the the bulk grand potential per unit volume and is given by

$$\beta J_{\mathrm{bulk}}^{vdW}=\frac{m^2}{4\pi }𝑑kk\left(\sqrt{k^2+1}k\right).$$
(35)
The mean-field contribution to the bulk grand-potential per unit volume is simply $`\beta J_{bulk}^{MF}=2\mu `$ since the mean-field solution in the bulk is just $`\psi =0`$; there are no surfaces to set up a mean-field potential. At this point we may not replace $`\mu `$ by $`\rho `$ because we need to work to one-loop for consistency. The total bulk grand-potential per unit volume is thus given by

$`\beta J_{\mathrm{bulk}}`$ $`=`$ $`2\mu +{\displaystyle \frac{m^2}{4\pi }}{\displaystyle 𝑑kk\left(\sqrt{k^2+1}k\right)}`$
$`=`$ $`2\mu {\displaystyle \frac{m^3}{12\pi }}+{\displaystyle \frac{1}{8\pi }}\mathrm{\Lambda }m^2+O({\displaystyle \frac{m^4}{\mathrm{\Lambda }}})`$
$`=`$ $`2\mu g{\displaystyle \frac{2\rho }{3}}\left(1{\displaystyle \frac{3\mathrm{\Lambda }}{2m}}\right)`$
where $`\mathrm{\Lambda }`$ is a momentum space cut-off corresponding to a short distance cut-off $`a1/\mathrm{\Lambda }`$ and $`g=m^3/8\pi \rho =ml_B`$. We see that indeed the expansion is in the dimensionless coupling $`g`$ as asserted in section II. The bulk density of electrolyte is given by

$$2\rho =\mu \frac{}{\mu }\beta J_{\mathrm{bulk}}=2\mu +\frac{m^3}{8\pi }\frac{1}{8\pi }\mathrm{\Lambda }m^2,$$

which can be written as

$$\mu =Z\rho ,Z=1\frac{g}{2}\left(1+\frac{\mathrm{\Lambda }}{m}\right).$$

From its definition in section II we then also have, to this order in $`g`$, that $`\mu _+^{}=Z\rho _+^{}`$.

Substituting this result into Eq. (IV) gives the well-known Debye expression for the bulk pressure

$$\beta P_{\mathrm{bulk}}=\beta J_{\mathrm{bulk}}=2\rho \frac{m^3}{24\pi }.$$
(37)
In the field theoretic formulation used here the surface charge (on one surface) per unit area, $`\sigma `$, is given by

$$\sigma =e\mu _+^{}\mathrm{exp}(ie\beta \varphi (z=0),$$
(38)
which becomes, to the order of accuracy of the present treatment,

$$\sigma =e\mu _+^{}\mathrm{exp}\left(e\beta \psi (z=0)\right)1+ie\beta \varphi ^{}(z=0)\frac{1}{2}e^2\beta ^2\varphi _{}^{}{}_{}{}^{2}(z=0),$$
(39)
where the average $``$ in the above equation is over the fluctuations $`\varphi ^{}`$. As the one-loop action in $`\varphi ^{}`$ is quadratic, the average of the term linear in $`\varphi ^{}`$ in Eq. (39) is zero and we may then write

$$\sigma =\frac{2\mu e\alpha ^{}(L)}{m}\frac{e\alpha ^{}(L)}{2}\frac{\beta J^{vdW}}{\alpha ^{}(L)}|_{\alpha ^{}=0}+O(\alpha _{}^{}{}_{}{}^{2}),$$
(40)
where we have used that $`\alpha =m\rho _+^{}/2\rho =m\mu _+^{}/2\mu `$ and where we have kept only the leading order behavior of the surface charge in $`\alpha ^{}`$. The next order terms can be calculated and are finite though one needs to eliminate certain artificial divergences dehoprep . The formula Eq. (40) gives a surface charge susceptibility with respect to the conjugate variable $`\alpha ^{}`$. We note that the first term in on the right hand-side of Eq. (40) is simply the mean-field contribution to the surface charge $`\sigma _{MF}`$.

To $`O(\alpha ^{})`$ we obtain

$`\sigma (L)`$ $`=`$ $`{\displaystyle \frac{2e\alpha ^{}(L)}{m}}(\mu {\displaystyle \frac{m^3}{8\pi }}{\displaystyle }{\displaystyle \frac{kdk}{D_+(k,m)}}`$ (41)
$`+`$ $`{\displaystyle \frac{m^3}{16\pi }}{\displaystyle }kdk{\displaystyle \frac{D_{}(k,m)}{D_+(k,m)[D_+(k,m)^2\mathrm{exp}(2Lm\sqrt{k^2+1})+D_{}(k,m)^2]}})+O(\alpha _{}^{}{}_{}{}^{2}),`$
where $`D_\pm (k,m)=kB(km)\pm \sqrt{k^2+1}`$. There is, however, a divergence in the first integral term in Eq. (41). This term corresponds to the van der Waals contribution to the charge of a bulk surface $`\sigma _{\mathrm{bulk}}=lim_L\mathrm{}\sigma `$. This divergence can be regularized by choosing the fugacity $`\mu `$ to give the desired bulk electrolyte density $`\rho `$ correct at one loop order. We define

$$\mathrm{\Gamma }=kdk(\frac{1}{kB(km)+\sqrt{k^2+1}}\frac{1}{2k},)$$
(42)
and then

$$\sigma _{\mathrm{bulk}}=\frac{2e\alpha ^{}}{m}\left(\mu \frac{m^3}{8\pi }\mathrm{\Gamma }\frac{m^2\mathrm{\Lambda }}{16\pi }\right),$$
(43)
where $`\mathrm{\Lambda }`$ is the ultra-violet cut-off introduced in the bulk calculation above. Note that for weak charging $`\alpha ^{}\alpha `$. Hence in terms of the physical variable $`\rho `$ we obtain the divergence-free formula for $`\sigma _{\mathrm{bulk}}`$

$$\sigma _{\mathrm{bulk}}=\frac{2e\alpha ^{}}{m}\left(\rho \frac{m^3}{16\pi }\frac{m^3}{8\pi }\mathrm{\Gamma }\right).$$
(44)
We remark here that in the case $`\mathrm{\Delta }0`$, if the Stern layer thickness $`h`$ is taken to zero then the term $`\mathrm{\Gamma }`$ in Eq. (44) diverges. It is clear however that one cannot have a surface charge exactly at the interface between two media of different dielectric constants due to the presence of arbitrarily close image charges. The divergence in $`h`$ as $`h0`$ in Eq. (44) is thus a physical divergence and any model using a surface charge must place this surface charge away from a discontinuity in the dielectric constant. When $`\mathrm{\Delta }=0`$ no such divergence is present and $`B(km)=1`$ leading to the simple formula

$$\sigma _{\mathrm{bulk}}=\left(1\frac{g}{6}\right)\sigma _{MF}(\mathrm{}).$$
(45)
We notice that from Eq. (37) that this equation may be written as

$$\sigma _{\mathrm{bulk}}=\frac{\beta P_{\mathrm{bulk}}e\alpha ^{}}{m}.$$
(46)
From Eq. (44) we see that effect of electrostatic interactions is to reduce the surface charge from the value it would have had without interactions. This is because the excess anions left in the bulk pull the cationic surface charge into the bulk. The case where $`\mathrm{\Delta }>0`$ (i.e. $`ϵ_0>ϵ`$) leads to $`B(km)1`$ for all $`k`$ and, examining the integrand in the formula defining $`\mathrm{\Gamma }`$, we find that $`\mathrm{\Gamma }<0`$ and hence that positive $`\mathrm{\Delta }`$ increases the surface charge above that of the case $`\mathrm{\Delta }=0`$. This is to be expected physically as the image charges in this case attract the ions towards the medium of higher dielectric constant lali . In the case where $`hm1`$ we may evaluate the integral defining $`\mathrm{\Gamma }`$ since the leading divergence as $`hm0`$ comes from the large $`k`$ integration. We find

$$\sigma _{\mathrm{bulk}}=\left(1\frac{g}{6}+\frac{g\mathrm{\Delta }}{4mh}\right)\sigma _{MF}(\mathrm{}).$$
(47)
Again, we see that for $`\mathrm{\Delta }>0`$ ($`\mathrm{\Delta }<0`$) the enhancement (reduction) of the surface charge which can be physically attributed to the presence of image charges.

Finally the $`L`$ dependence of the surface charge at $`O(\alpha ^{})`$ is given by

$$\sigma (L)=\sigma _{MF}(L)\left(1\frac{g}{2}g\mathrm{\Gamma }+\frac{g}{2}k𝑑k\frac{D_{}(k,m)}{D_+(k,m)[D_+(k,m)^2\mathrm{exp}(2Lm\sqrt{k^2+1})+D_{}(k,m)^2]}\right),$$
(48)
where $`D_\pm (k,m)=kB(km)\pm \sqrt{k^2+1}`$.

Thus, because $`\alpha ^{}(L)0`$ as $`L0`$, we find that $`\sigma _{MF}`$, and hence the surface charge $`\sigma `$, vanishes as the film becomes thin. This is a physical result which is not picked up by a pure Gaussian theory deho .

As previously stated the total disjoining pressure is composed of a mean-field contribution and a contribution coming from the fluctuations. We find the total of these two terms gives

$$P_d(L)=\frac{\sigma _{MF}^2(L)}{2ϵ\mathrm{sinh}^2(\frac{mL}{2})}\left(1+\frac{2(\sigma (L)\sigma _{MF}(L))}{\sigma _{MF}(L)(1+\alpha ^{}(L)\mathrm{coth}(\frac{mL}{2}))}\right)4g\rho k_BT𝑑kk\sqrt{k^2+1)}\frac{f^2(k)}{1f^2(k)},$$
(49)
where

$$f(k)=\frac{kB(km)+\alpha ^{}(L)\sqrt{k^2+1}}{kB(km)+\alpha ^{}(L)+\sqrt{k^2+1}}\mathrm{exp}\left(Lm\sqrt{k^2+1}\right).$$
(50)
In the derivation of this formula the divergences which arise at intermediate stages of the calculation can, as in the case of the surface charge, be shown to cancel in the final result.

The first term in Eq. (49) is simply the mean-field contribution to $`P_d`$, the second (in the same bracket) is the contribution coming from the dependence of $`J^{vdW}`$ on $`L`$ via the $`L`$ dependence of $`\alpha ^{}`$. The last term is a form of screened zero frequency van der Waals contribution. In the absence of electrolyte we find that this last term gives a $`1/L^3`$ Casimir attraction across the film. In the presence of electrolyte this interaction is screened mani  and decays exponentially as $`\mathrm{exp}(2mL)`$ which is twice as quickly as the mean-field contribution to the disjoining pressure which decays as $`\mathrm{exp}(mL)`$ for large $`L`$. However in the theory presented here, the fluctuation effects give an additional term which decays also as $`\mathrm{exp}(mL)`$ and hence the fluctuations modify the long distance behavior of $`P_d`$. We note theories with fixed surface charge the long-range component of the disjoining pressure is not altered at two-loop level and this effect is specific to charge regularized models. The strength and sign of this long range modification of $`P_d`$ is controlled the ratio $`(\sigma (L)\sigma _{MF}(L))/\sigma _{MF}(L)`$ which measures the relative deviation of the surface charge from its mean-field value. If the fluctuation effects enhance (reduce) the surface charge then the long range value of $`P_d`$ is increased (decreased) from its mean-field value. The Casimir term is, however, is always attractive.

It should be remarked at this stage that to this order, $`O(g)`$, there will be $`L`$-dependent contributions from the non-Gaussian interaction term in $`\varphi _{}^{}{}_{}{}^{4}`$. These contributions can be shown to vanish as $`L\mathrm{}`$ but their effect for finite $`L`$ must be calculated. However, such a calculation requires the apparatus for the general perturbation theory to be developed which we shall present in a forthcoming paper dehoprep .

## V Discussion and Conclusion

We have systematically developed a theory for a thin film with a full non-linear surface charging mechanism while retaining the free field theory description for the bulk electrostatic fields. This corresponds to using linear Debye theory in the bulk with fugacity $`\mu `$ but with the fully interacting description of the sources for the charging mechanism of the surfaces. We have applied the theory to a model consisting of a triple layer system, shown in Fig. (1), in which there is adsorption of cations on to the surface modelled by a surface fugacity $`\mu _+^{}`$ and encoded in the dimensionless surface absorption strength parameter $`\alpha =m\rho _+^{}/2\rho `$ where $`\rho `$ and $`\rho _+^{}`$ are the bulk density and cation density on the surface of a bulk region, respectively, and $`m`$ is the Debye mass. At the surface there is a Stern layer of thickness $`h`$ from which all ions are excluded. The film is of thickness $`L`$ and the dielectric constants are $`ϵ80ϵ_0`$ in the film and $`ϵ_0`$ outside the film. This model for a real surface is too simple but it encodes the important feature that the thermodynamic properties of the film are very strongly dependent on the detailed nature of the surface and its properties. This is due to two features: the charging mechanism which allows the surface charge to remain in equilibrium with the interior charges and the effect of image charges due to the discontinuity in the dielectric constant at the surface. First we determine the mean-field solution $`\varphi _c(z)`$ using the non-linear surface operators as the source and then we use the Schrödinger kernel approach to calculate the partition function as an expansion in $`\alpha `$ and $`g=ml_B`$ where $`l_B`$ is the Bjerrum length. Much of the details of this approach have been discussed in an earlier paper deho . In this paper, we concentrate on the effects of the non-linear surface charging mechanism which leads us to introduce an effective, or running, surface charging parameter $`\alpha ^{}(L)`$ and we analyze the behavior of the surface charge $`\sigma (L)`$ and the disjoining pressure $`P_d(L)`$ on $`m,\alpha `$ and $`h`$. The formulas summarizing our findings are Eqs. (48) and (49). Examples of the solutions to these equations are shown in Figs. (4) to (12) and we now briefly discuss the salient features of these results.

In Figs. (2) and (3) we show $`\alpha ^{}(L)`$ as a function of $`L`$ for various values of $`\alpha `$ and $`m`$, respectively. $`\alpha ^{}(L)`$ controls the strength of the surface charging mechanism and from Eq. (16), and what follows, it is clear that $`\alpha ^{}(L)0`$ as $`L0`$ which in turn causes $`\sigma _{MF}`$ and $`\sigma `$ to vanish also in this limit.

In Figs. (4) to (6) we show the dependence of $`P_d`$ on $`h,m,\alpha `$, respectively. From all these figures we see that the characteristic collapse transition is evident but that its strength is very sensitive to the parameters. In particular, from Fig. (4) we see that $`P_d`$ decreases as $`h`$ decreases, as we should expect since the image charges at the surface are repelling the cations and so reducing the surface charge. This effect can be seen directly in Fig.(9). The effect on $`P_d`$ is due to the $`\sigma `$ dependent term in Eq. (49) which arises because of the implicit $`L`$ dependence of the free energy through its dependence on $`\alpha ^{}(L)`$. Note that $`\sigma _{MF}(L)`$ is independent of $`h`$ as in this formulation the effect of image charges first comes in at the one-loop level. The dependence of $`P_d`$ on $`m`$ and $`\alpha `$ shown in Figs. (5) and (6) has the expected trends but again the height of the peak in $`P_d(L)`$ is strongly dependent on the parameters which have been chosen to take values that can typically be achieved in experiment. In Fig. (7) we show the mean-field component and one-loop contributions for typical parameter values.

In Figs. (9) to (11) the behavior of the surface charge $`\sigma (L)`$ is shown. We see from Fig (9) that $`\sigma (L)`$ decreases very strongly with $`L`$ for small $`L`$ and that as $`h`$ decreases the effect strengthens and that for sufficiently small $`h`$ the value of $`\sigma (L)`$ has a zero and becomes negative. Ultimately, $`\sigma (L)0`$ as $`L0`$ and so must have a minimum value before turning towards the origin. These effects are due to the one-loop term in Eq. (48) and can be seen clearly in Fig. (12) where the mean-field and one-loop contributions to $`\sigma (L)`$ are separately shown. In Figs. (10) and (11) the trends shown are as expected but, as in the case of $`P_d`$ the magnitude of $`\sigma (L)`$ is very sensitive to parameter values. The overall prediction is that $`\sigma (L)`$ is strongly dependent on $`L`$ and vanishes as $`L0`$.

In Fig. (8) we compare $`P_d`$ for the linearized theory from (deho ) and the non-linear theory of this paper with $`h=0.3nm`$. Although the peak in $`P_d`$ occurs in much the same place it is lower in the non-linear theory for this value of $`h`$. Since the peak height is strongly dependent on $`h`$ we see that a quantitative prediction requires a realistic model for the surface. See Fig. (9).

An important feature of these calculations is to note that the results are expressed as a series in both $`\alpha `$ or $`\alpha ^{}(L)`$ and $`g=ml_B`$ with partial resummations in some cases. The major approximation is to use the free field theory within the bulk. The object was to study the effects of the non-linear surface charging mechanism and we have shown that these effects are indeed strong and it is clear that any approach which omits them or assumes a constant surface charge will be incorrect. Some of the effects are strong and there are features, such as the minimum in $`\sigma (L)`$ and its change of sign, that must be studied further in the full non-linear theory to see if they are not artifacts of the approximation. A consistent control over spurious and artificial infinities must await the full perturbation theory. An example is eluded to in Eq. (40) and what follows. We have indicated how to control such quantities here to the one-loop level and see that even here the analysis is rather delicate. There are, in principle, $`O(g)`$ terms from interactions within the bulk which will vanish as $`L\mathrm{}`$ but contribute finite $`L`$ effects to $`P_d`$ and $`\sigma `$ but these terms are not expected to be large. We shall present an analysis of all these topics in a forthcoming paper dehoprep  in which the full non-linear theory and its perturbation expansion will be studied.