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# Effective charge saturation in colloidal suspensions

## I Introduction

When a solid-like object, say a colloidal particle (polyion), which carries a large number of ionisable groups at the surface is immersed in a polarizable medium (with a dielectric constant $`ϵ`$, say water), the ionisable groups dissociate, leaving counter-ions in the solutions and opposite charges at the surface. The interactions between the charged colloids, which determine the phase and structural behaviour of the suspension, is mediated by the presence of micro-ions clouds. The complete description of the system is thus a formidable task in general. However in view of the large asymmetry of size and charge between macro- and micro- ions, one expects to be able to integrate out the micro-ions degrees of freedom, and obtain an effective description involving macro-ions only. In the pioneering work of Derjaguin, Landau, Verwey and Overbeek , micro-ions clouds are treated at the mean-field Poisson-Boltzmann (PB) level, yielding the foundations of the prominent DLVO theory for the stability of lyophobic colloids. An important prediction of the theory is the effective interaction pair potential between two spherical colloids of radii $`a`$ in a solvent which, within a linearization approximation, takes the Yukawa or Debye-Hückel (DH) form:

$$v(r)=\frac{Z^2e^2}{4\pi ϵ}\left(\frac{\mathrm{exp}[\kappa a]}{1+\kappa a}\right)^2\frac{\mathrm{exp}(\kappa r)}{r},$$
(1)
where $`Z`$ is the charge of the object in units of the elementary charge $`e`$ and $`\kappa `$ denotes the inverse Debye screening length. The latter is defined in terms of the micro-ions densities {$`\rho _\alpha `$} (with valences {$`z_\alpha `$}) as: $`\kappa ^2=4\pi \mathrm{}_B_\alpha \rho _\alpha z_\alpha ^2`$. The Bjerrum length $`\mathrm{}_B`$ is defined as $`\mathrm{}_B=e^2/(4\pi ϵk_BT)`$, where $`ϵ`$ is the permittivity of the solvent considered as a dielectric continuum: $`\mathrm{}_B=7`$Å for water at room temperature.

However, this approach becomes inadequate to describe highly charged objects for which the electrostatic energy of a micro-ion near the colloid surface largely exceeds $`k_BT`$, the thermal energy, because the linearization of the PB equations is a priori not justified. In this case however, the electrostatic potential in exact  or mean-field  theories still takes the Debye-Hückel like form far from the charged bodies, provided that the bare charge $`Z`$ is replaced by an effective or renormalized quantity $`Z_{\text{eff}}`$. The micro-ions which suffer a high electrostatic coupling with the colloid accordingly accumulate in its immediate vicinity so that the decorated object, colloid plus captive counter-ions, may be considered as a single entity which carries an effective charge $`Z_{\text{eff}}`$, much lower (in absolute value) than the structural one. Within the prominent mean-field PB theory  –often quite successful despite of its limitations–, $`Z`$ and $`Z_{\text{eff}}`$ coincide for low values of the structural charge, but $`Z_{\text{eff}}`$ eventually reaches a saturation value $`Z_{\text{eff}}^{\text{sat}}`$ independent of $`Z`$ when the bare charge increases . Arguably, the difference $`ZZ_{\text{eff}}`$ is identified with the amount of counter-ions “captured” or “condensed”  onto the macro-ion.

A reminiscent effect has been recognized in the physics of polyelectrolytes under the name of Manning-Oosawa condensation. Here, the object is an infinitely long and thin rod bearing $`\lambda `$ charges per unit length. At infinite dilution and in the absence of salt, it can be shown at the PB level that the polyelectrolyte is electrostatically equivalent to a rod carrying $`\lambda _{\text{equiv}}`$ charge per unit length, where the equivalent charge density saturates to a critical value $`\lambda _{\text{equiv}}=1/\mathrm{}_B`$ when $`\lambda `$ increases . In general however, PB theory can be solved analytically in very few geometries only and the difficulty remains to predict $`Z_{\text{eff}}`$ for a given colloidal system . In the absence of a general analytical framework for the computation of the effective charge, this quantity is often considered as an adjustable parameter to fit experimental data .

The aim of the present paper is to propose a method that allows to compute effective charges comparing favorably with PB in the saturation regime, provided the size $`a`$ of the charged macro-ion is much larger than Bjerrum length $`\mathrm{}_B`$ and screening length $`\kappa ^1`$. In the infinite dilution limit, we define the effective charges from the large distance behaviour of the electrostatic potential created by the (isolated) macro-ion . While other definitions have been put forward  this choice is relevant in view of computing a macro-ion pair potential at large distances, in the spirit of the DLVO approach . It moreover avoids the ambiguity of introducing a cutoff region in space which interior containing the colloid would exactly enclose a total charge equal to the effective one. At leading order in curvature $`(\kappa a)^1`$, our method easily provides effective charges at saturation close to their counterparts obtained in PB theory. In the situation of finite colloid concentration where it is no longer obvious to extract an effective charge from the large distance behaviour of the electrostatic potential computed within a non-linear theory, we follow the proposition put forward by Alexander et al.  introducing a Wigner-Seitz cell. In this situation, we generalize our original method into a prescription that we successfully test in various geometries, for different thermodynamic conditions (isolated systems or in contact with a salt reservoir).

The paper is organized as follows. We first recall the basic framework of PB theory in section II. We then examine in some details the simple case of a spherical polyion in the infinite dilution limit (section III). This example allows us to devise a general method to compute the effective charge for arbitrary colloidal systems. The situation of finite density of colloids is then examined introducing Wigner-Seitz cells. The salt free case is developed in section IV, while the situation of finite ionic force is explicited in section V. We finally confront the results obtained within our prescription with experimental or simulation data in various geometries in section VI. We discuss the general validity of our mean-field treatment relying on PB approximation in section VII and conclusions are drawn in section VIII. The preliminary results of this study have been published elsewhere .

## II General Framework: Poisson-Boltzmann theory

Poisson-Boltzmann theory provides a mean field description of the micro-ions clouds in the presence of the polyions, acting as an external potential. The key approximation in the approach is the neglect of (micro-)ionic correlations. The size of the micro-ions with density $`\rho `$ is neglected as well and the chemical potential reduces to its ideal contribution $`\mu =k_BT\mathrm{ln}(\rho \mathrm{\Lambda }^3)`$, where $`\mathrm{\Lambda }`$ is an irrelevant length scale. Without loss of generality, the macro-ions are supposed to be positively charged.

At equilibrium the electro-chemical potential of the micro-ions is uniform over the system. Introducing the reduced electrostatic potential $`\varphi =eV/k_BT`$, the equilibrium condition for micro-ions thus reads at the mean field level

$$\mathrm{ln}(\rho ^\pm \mathrm{\Lambda }^3)\pm \varphi =\mathrm{ln}(\rho _0\mathrm{\Lambda }^3)$$
(2)
where $`\{\rho ^{},\rho ^+\}`$ are the density fields of the charged micro-species (counter-ions and co-ions), which we assume for simplicity mono-valent. The constant $`\rho _0`$ will be specified hereafter. We restrict here to mono-valent micro-ions (both counter-ions and salt). For higher valences, the reliability of PB deteriorates (see section VII). The equilibrium condition, Eq. (2), is closed by Poisson’s equation for the electrostatic potential

$$^2\varphi =4\pi \mathrm{}_B\left(\rho ^+\rho ^{}\right).$$
(3)
The gradient of equation (2) expresses the condition of mechanical equilibrium for the fluid of micro-ions . At this level, one has to separate between the no-salt and finite ionic strength cases.

* No-Salt Case Only the released (here negative) counter-ions are present in the system. The PB equation for the reduced potential thus reads

$$^2\varphi =\kappa ^2e^\varphi $$
(4)
where the screening constant $`\kappa `$ is defined as $`\kappa ^2=4\pi \mathrm{}_B\rho _0`$, with $`\rho _0`$ the constant introduced in Eq. (2). The latter is fixed by the electroneutrality condition, which imposes

$$_𝒱𝑑𝒓\rho ^{}(𝒓)=ZeN_c$$
(5)
with $`N_c`$ the number of (identical) macro-ions, of charge $`Ze`$, contained in the volume $`𝒱`$. The quantity $`\rho _0`$ is a Lagrange multiplier associated with the electroneutrality condition and has no specific physical meaning; it is modified by a shift of potential, which can be chosen at our convenience to fix $`\varphi `$ at a given point in the solution.
* Finite Ionic strength situation In the finite ionic strength case, salt is added to the solution, so that both co- and counter- ions are present in the system. In the following we shall work in the semi-grand ensemble, where the { colloids+micro-ions } system is put in contact with a reservoir fixing the chemical potential of the micro-ions $`\mu _0`$. In this case $`\rho _0`$ in Eq. (2) is the concentration of salt in the reservoir (where $`\varphi `$ is conveniently chosen to vanish), so that $`\mu _0=k_BT\mathrm{ln}(\rho _0\mathrm{\Lambda }^3)`$. Since we are considering mono-valent micro-ions $`\rho _0`$ coincides with the ionic strength of the reservoir which is generally defined as $`I_0=n_\alpha ^1_\alpha z_\alpha ^2\rho _\alpha ^0`$ for a number $`n_\alpha `$ of micro-ions species with valences $`z_\alpha `$ and reservoir densities $`\rho _\alpha ^0`$. This results in the PB equation for the reduced potential $`\varphi `$

$$^2\varphi =\kappa ^2\mathrm{sinh}\varphi $$
(6)
where the screening factor $`\kappa `$ is now defined in terms of the micro-ion concentration in the reservoir $`\kappa ^2=8\pi \mathrm{}_BI_0\kappa _{\text{res}}^2`$.

In addition to these two situations, we shall also consider the case of infinite dilution where an isolated macro-ion is immersed in an electrolyte of given bulk salt concentration $`I_0`$ which thus plays the role of a reservoir.

PB equations, (4) or (6), are supplemented by a set of boundary conditions on the colloids, expressing the relationship between the local electric field and the bare surface charges of the colloidal particles, $`\sigma e`$. This gives the boundary condition for $`\varphi `$ at the surface of the colloid in the form

$$(\mathbf{}\varphi )\widehat{𝐧}=4\pi \mathrm{}_B\sigma ,$$
(7)
where $`\widehat{𝐧}`$ denotes a unit vector normal to the colloid’s surface. Except in simple isotropic geometries , the analytical solution of PB theory is not known.

## III Infinite dilution limit: asymptotic matching for the effective charge

In this section, after recalling a few results on the planar case, we explicit our method on the particular example of spheroids. We then generalize it to an arbitrary colloidal object and consider the case of charged rods as an application. We work in the infinite dilution limit, and therefore, we reject the external boundaries of the system at infinity.

### A Planar Case

In the case of the planar geometry, the non linear PB equation can be analytically solved. The detailed solution is given in appendix A. The important result however is that far from the charged plane, the solution of the PB equation reduces to that of the LPB equation :

$$\varphi _{_{\text{PB}}}(z)\varphi _Se^{\kappa z}$$
(8)
The apparent potential $`\varphi _S`$ is equal to $`\varphi _S=4`$ in the limit of high bare charge of the plane.

In this limit, the fixed charge boundary condition is therefore replaced on the plane by an effective fixed surface potential boundary condition $`\varphi _{_{\text{LPB}}}(z=0)=\varphi _S=4`$. The effective charge density (in the saturation -high bare charge- limit) is then computed using Gauss theorem at the surface, yielding

$$\sigma _{\text{eff}}^{\text{sat}}=\frac{\kappa }{\pi l_B}.$$
(9)
### B Charged spheres

Let us now consider a highly charged isolated sphere (bare charge $`Ze`$, radius $`a`$) immersed in a symmetric 1:1 electrolyte of bulk ionic strength $`I_0`$. Within PB theory, the dimensionless electrostatic potential obeys equation (6). Suppose we know the exact solution $`\varphi _{_{\text{PB}}}(r)`$ (in spherical coordinates with the origin at the center of the sphere), and the bare charge $`Z`$ is large enough so that the reduced electrostatic potential at contact, $`\varphi _{_{\text{PB}}}(a)`$, is (much) larger than 1. Then, we can divide the space surrounding the polyion into two sub-regions: a non-linear region (close to the particle’s boundary) where $`\varphi _{_{\text{PB}}}(r)>1`$, and a linear region where $`\varphi _{_{\text{PB}}}(r)<1`$ (the potential vanishes at infinity). The surface delimiting these two regions is a sphere of radius $`r^{}`$ such that $`\varphi _{_{\text{PB}}}(r^{})1`$.

Far from colloid, the complicated non-linear effects have died out to a substantial degree, and the solution also obeys the linearized Poisson-Boltzmann (LPB) equation $`^2\varphi =\kappa ^2\varphi `$, and therefore takes the Yukawa form

$$\varphi _{_{\text{LPB}}}(r)=\frac{Z_{\text{eff}}}{(1+\kappa a)}\mathrm{}_B\frac{e^{\kappa \left(ra\right)}}{r}.$$
(10)
The effective charge $`Z_{\text{eff}}`$ is defined here without ambiguity from the far field behaviour of $`\varphi _{_{\text{PB}}}(r)`$:

$$\underset{r\mathrm{}}{lim}\varphi _{_{\text{LPB}}}(r)/\varphi _{_{\text{PB}}}(r)=\mathrm{\hspace{0.17em}1}.$$
(11)
In practice, $`\varphi _{_{\text{LPB}}}`$ and $`\varphi _{_{\text{PB}}}`$ coincide in the linear region ($`rr^{}`$), so that $`\varphi _{_{\text{LPB}}}(r^{})1`$ (i.e. is a quantity of order one).

When $`a\kappa ^1`$, the non-linear effects are confined to the immediate vicinity of the macro-ion, with an extension $`\kappa ^1`$. We therefore have $`r^{}/a1`$ and as a consequence, $`\varphi _{_{\text{LPB}}}(r=a)\varphi _{_{\text{LPB}}}(r^{})1`$. We thus obtain the effective boundary condition that $`\varphi _{_{\text{LPB}}}`$ is a quantity $`𝒞`$ of order one for $`r=a`$; from Eq. (10) this means that $`Z_{\text{eff}}^{\text{sat}}=𝒞a(1+\kappa a)/\mathrm{}_B`$. This simple argument provides the non trivial dependence of the effective charge at saturation upon physico-chemical parameters; it applies in the saturation regime of PB theory where $`Z_{\text{eff}}=Z_{\text{eff}}^{\text{sat}}`$ and assumes that the bare charge $`Z`$ is high enough so that the non-linear region exists. In order to determine the constant $`𝒞`$, we may consider the planar limit $`a\mathrm{}`$ where the analytical solution of PB theory is known (see above and appendix A): the surface charge density $`Z_{\text{eff}}^{\text{sat}}/(4\pi a^2)`$ should coincide with that of a charged plane $`\kappa /(\pi \mathrm{}_B)`$, Eq. (9). This imposes that $`𝒞=4`$ and going back to the charge:

$$Z_{\text{eff}}^{\text{sat}}=\frac{4a}{\mathrm{}_B}(1+\kappa a).$$
(12)
In de-ionized solutions, this argument leads to the scaling $`Z_{\text{eff}}^{\text{sat}}a/\mathrm{}_B`$, which has been recently tested for various latex colloids .

The physical argument leading to (12) may be rationalized as follows. The situation of large $`\kappa a`$ corresponds to a low curvature limit where the solution of Eq. (6) may be approximated by the solution of the planar problem in the region where curvature effects may be neglected : the latter corresponds to a region $`a<r<a+\delta a`$, with $`\delta aa`$. It is crucial to note that $`r^{}<a+\delta a`$ since, as mentioned above, the extension of the region where the non linear effects are important (defining $`r^{}`$) has an extension of order $`\kappa ^1`$, smaller than $`\delta aa`$ in the limit of large $`\kappa a`$. As a consequence, in the region $`r^{}<r<a+\delta a`$, the solution of the LPB equation, Eq. (10), may be matched to the asymptotic expression of the planar solution, given in Eq. (8) (using $`ra`$ and $`zra`$). The expression (12) is therefore recovered, showing again that at the linearized level, the apparent potential is $`\varphi _{_{\text{LPB}}}(a)=4`$ in the saturation limit.

Eq. (12) provides by construction the correct large $`\kappa a`$ behaviour of $`Z_{\text{eff}}^{\text{sat}}`$, and becomes exact (compared to PB) in the planar limit. We will show below that it remains fairly accurate down to $`\kappa a`$ of order 1. A similar expression may be found in , but the generality of the underlying method does not seem to have been recognized. This result is supported by the work of Oshima et al.  which proposes an approximation scheme of the non-linear PB equations for spheres in infinite dilution, for large $`\kappa a`$. In particular these authors obtain an analytical approximation for the apparent potential at the colloid surface, which reads in the saturation regime:

$$\varphi _S^{\text{Osh}}=\mathrm{\hspace{0.17em}\hspace{0.17em}8}\frac{1+\kappa a}{1+2\kappa a}.$$
(13)
Supplemented with expression (10), this leads to the improved effective charge

$$Z_{\text{eff}}^{\text{sat}}=\frac{8a}{\mathrm{}_B}\frac{(1+\kappa a)^2}{1+2\kappa a}.$$
(14)
In the limit of large $`\kappa a`$ where $`\varphi _S4`$, both Eqs. (12) and (14) have the same behaviour.

In order to test the validity of these results, we have numerically solved the full non-linear PB equation, Eq. (6) and computed the effective charge from the electrostatic potential at large distances, i.e. the value required to match $`\varphi _{_{\text{LPB}}}`$ to the far field $`\varphi _{_{\text{PB}}}`$ obtained numerically. For each value of $`\kappa a`$, we make sure to consider large enough bare charges in order to probe the saturation regime of $`Z_{\text{eff}}`$. Figure 1 compares the numerical PB saturation value of the effective charge to the prediction of our approach, Eq. (12), and to that obtained using the results of Oshima et al., Eq. (14). We see that Eq. (14) provides an accurate estimate for $`Z_{\text{eff}}^{\text{sat}}`$ as a function of $`\kappa a`$, for $`\kappa a1`$. Working at the level of our approach only, Eq. (12) still yields a reasonable estimate for $`Z_{\text{eff}}^{\text{sat}}(\kappa a)`$, specially for high values of the parameter $`\kappa a`$. In the limit of small $`\kappa a`$, both expressions (12) and (14) differ notably from the PB saturation charge which diverges, as shown by Ramanathan , as:

$$Z_{\text{eff}}^{\text{sat}}\frac{a}{\mathrm{}_B}\left\{2\mathrm{ln}(\kappa a)+2\mathrm{ln}[\mathrm{ln}(\kappa a)]+4\mathrm{ln}2\right\}\text{for}\kappa a0.$$
(15)
At this point, it is instructive to briefly reconsider the work of Squires and Brenner  who demonstrated that the attractive interactions between like-charged colloidal spheres near a wall could be accounted for by a non-equilibrium hydrodynamic effect (see also ). In their analysis, they used an ad hoc value of 0.4 for the ratio $`\sigma _{\text{glass}}/\sigma _{\text{sphere}}`$ of surface charge densities of planar and spherical polyions, in order to capture the one-wall experiment of Larsen and Grier . This was the only free parameter in their approach. From Eqs. (A6) and (14) for the saturation values, we easily obtain

$$\frac{\sigma _{\text{glass}}}{\sigma _{\text{sphere}}}=\frac{\kappa a(1+2\kappa a)}{2(1+\kappa a)^2}.$$
(16)
In the experiment of , we have $`\kappa a1.2`$ \[larger than 1, so that (14) is reasonably accurate\], and we obtain $`\sigma _{\text{glass}}/\sigma _{\text{sphere}}0.42`$: it is thus possible to justify the choice made in  assuming that both the confining wall and the pair of colloids are charged enough to sit in the saturation regime. In this respect, knowledge of their bare charges is unnecessary.

### C Arbitrary colloidal object

Generalizing this analysis for an arbitrary colloidal object (of typical size $`a`$), we propose the following method to estimate the effective charge in the limit of large values of $`\kappa a`$:

1. Solve the LPB equation for the geometry under consideration
2. Define the saturation value, $`Z_{\text{eff}}^{\text{sat}}`$, such that the linear reduced potential at contact is a constant, $`𝒞`$, of order unity

$$\left|\varphi _S\varphi _{\text{bulk}}\right|=𝒞,$$
(17)
where the asymptotic matching with the planar case yields $`𝒞=4`$.
3. If one is interested in the effective charge for arbitrary and possibly small bare charges, a crude approximation follows from

$`Z_{\text{eff}}`$ $`=`$ $`ZZZ_{\text{eff}}^{\text{sat}}`$ (18)
$`Z_{\text{eff}}`$ $`=`$ $`Z_{\text{eff}}^{\text{sat}}ZZ_{\text{eff}}^{\text{sat}}.`$ (19)

Our approach has several advantages. First, we do not need to solve the full non-linear PB equations to obtain the effective charge. Second, the proposed method provides an analytical prediction for $`Z_{\text{eff}}^{\text{sat}}`$. Third, our approach is easily adapted to other macro-ion geometries or finite dilutions, unlike that of Ref.  (even if these authors could find an equivalent of expression (13) for cylinders, see below).

In the following, we will mainly focus on the high bare charge limit of the colloids where the effective charge reaches a saturation plateau, $`Z_{\text{eff}}^{\text{sat}}`$. In order to simplify notations, we will denote this saturation value $`Z_{\text{sat}}`$.

### D Rod-like macro-ions

Now the object is an infinitely long cylinder (radius $`a`$, bare line charge density $`\lambda e`$). The solution of linear PB equation is (in cylindrical coordinates where $`r`$ is the distance to the axis)

$$\varphi (r)=2\lambda \mathrm{}_B\frac{1}{\kappa a}\frac{K_0(\kappa r)}{K_1(\kappa a)},$$
(20)
where $`K_0`$ and $`K_1`$ are (respectively) the zero and first order modified Bessel functions of the second kind. Hence the apparent potential is

$$\varphi _S=2\lambda \mathrm{}_B\frac{1}{\kappa a}\frac{K_0(\kappa a)}{K_1(\kappa a)}$$
(21)
Setting $`\varphi _S=𝒞=4`$ yields our estimate for the effective line charge density at saturation

$$\lambda _{\text{sat}}=\frac{2\kappa a}{\mathrm{}_B}\frac{K_1(\kappa a)}{K_0(\kappa a)}.$$
(22)
In the limit of large values of the bare line charge density $`\lambda `$, Oshima et al. obtained an approximate expression for the apparent potential in the saturation regime (based on an approximation scheme for the PB equation, see Appendix A of Ref. ):

$$\varphi _S^{\text{Osh}}=8\frac{K_1(\kappa a)}{[K_0(\kappa a)+K_1(\kappa a)]}$$
(23)
As expected, we note that $`\varphi _S^{\text{Osh}}4`$ in the limit $`\kappa a1`$. However, from Eq. (23), we deduce an improved estimate of $`\lambda _{\text{sat}}`$

$$\lambda _{\text{sat}}=\frac{4\kappa a}{\mathrm{}_B}\frac{K_1(\kappa a)}{K_0(\kappa a)}\frac{K_1(\kappa a)}{[K_0(\kappa a)+K_1(\kappa a)]}.$$
(24)
In Fig. 2, we display $`\mathrm{}_B\lambda _{\text{sat}}`$ \[estimated either with Eq. (22) or Eq. (24)\] as a function of $`\kappa a`$, together with the “exact” value of $`\mathrm{}_B\lambda _{\text{sat}}`$ found by solving the full non-linear PB equation for high bare charges in the saturation regime. Note that the plot is in log-linear scale, in order to emphasize the small $`\kappa a`$ region where our method is not a priori expected to work. Surprisingly, the agreement between the numerical result of the full PB equation and (24) is satisfactory down to very low values of $`\kappa a`$, $`\kappa a10^2`$, although the two quantities have a different asymptotic behaviour: the exact $`\mathrm{}_B\lambda _{\text{sat}}`$ is finite when $`\kappa a0`$ ($`\mathrm{}_B\lambda _{\text{sat}}=2/\pi `$ from ref. , see next paragraph), whereas both estimate Eq. (22) and (24) vanish, although extremely slowly (as $`1/\mathrm{log}(\kappa a)`$).

Importantly, $`\kappa a0`$ is the asymptotic regime where the celebrated Manning limiting law  happens to be exact, and the condensation criterion holds. In this limit, above the condensation threshold, the electrostatic potential solution of the full non-linear PB equation is indistinguishable from that of a cylinder carrying a line charge density $`\lambda _{\text{equiv}}=1/\mathrm{}_B`$ . The two quantities $`\lambda _{\text{equiv}}`$ and $`\lambda _{\text{sat}}`$ may be coined as “effective charges”, but we maintain our initial definition of the effective charge from the far field potential solution of the non-linear PB equation. In this respect, $`\lambda _{\text{equiv}}\lambda _{\text{sat}}`$, (as already discussed in the Appendix of reference ). This is because one expects a remnant non-linear screening of $`\lambda _{\text{equiv}}`$, so that $`\lambda _{\text{sat}}<\lambda _{\text{equiv}}=1/\mathrm{}_B`$. The limiting situation $`\kappa a0`$ has been solved recently within Poisson-Boltzmann theory, using exact results from the theory of integrable systems . The corresponding solution illustrates our point. This seminal work allows to compute explicitly the effective charge, which reads

$$\underset{\kappa a0}{lim}\lambda _{\text{eff}}=\frac{2}{\pi \mathrm{}_B}\mathrm{sin}\left(\frac{\pi }{2}\lambda \mathrm{}_B\right).$$
(25)
Accordingly, when $`\lambda `$ exceeds the Manning threshold $`1/\mathrm{}_B`$, the effective charge saturates to a value

$$\lambda _{\text{sat}}=\frac{2}{\pi \mathrm{}_B}\frac{0.6366}{\mathrm{}_B}<\lambda _{\text{equiv}}=\frac{1}{\mathrm{}_B}.$$
(26)
It is noteworthy that the limit $`2/(\pi \mathrm{}_B)`$ (compatible with the numerical results reported by Fixman, see for example Fig. 1 of ref. ) is reached extremely slowly as $`\kappa a`$ is decreased, in practice for $`\kappa a<10^6`$. For example, for $`\kappa a=10^2`$, the numerical solution of the PB equation yields $`\lambda _{\text{sat}}0.81/\mathrm{}_B`$, hence a value 30% larger than the asymptotic limit.

## IV Effective charge at finite concentration. The no-salt case

The situation of finite density of colloids does not allow to define an effective charge from the far field of a single body potential, as done in section III. Here, we rely on the proposition put forward by Alexander et al. to define an effective charge . We recall here the main points of this PB cell approach. First, the procedure makes use of the concept of Wigner-Seitz (WS) cells: the influence of the other colloids is accounted for by confining the macro-ion into a cell, with global electroneutrality . The size of the cell, $`R_{WS}`$ is computed from the density of colloids, while its geometry is chosen as to mimic the spatial structure of the colloids in the solution. Second, the “effective” potential solution of the linearized PB equation is such that the linear and non-linear solutions match up to the second derivative at the boundaries of the WS cell (hence they match up to at least the third derivative because of electroneutrality in “isotropic” –spherical or cylindrical– cells). Note that in the original paper of Alexander et al.  the procedure was introduced to obtain the effective charge from the *numerical* solution of the non linear PB equation. But in the present work we shall use the approach to get effective charges at the LPB level together with our prescription. Such a route has proven successful for mono-valent micro-ions, see e.g. , and it has been shown recently that similar ideas could be employed to describe discrete solvent effects (again for mono-valent micro-ions ).

In this section, we generalize the analysis proposed in section III C to find a prescription suitable to treat the case of finite concentration of colloids. We eventually compare our results to those obtained following ref. , for planar, cylindrical and spherical geometries.

### A Generalized prescription and planar test case

In the infinite dilution case, the reference potential is the bulk one $`\varphi _{\text{bulk}}`$. The natural generalization of this choice for the finite concentration case consists in replacing in Eq. (17) $`\varphi _{\text{bulk}}`$ by $`\varphi __\mathrm{\Sigma }`$ the reduced electrostatic potential at the boundary of the WS cell. Hence, we propose

$$\left|\varphi _S\varphi __\mathrm{\Sigma }\right|=𝒞.$$
(27)
If added salt was present in the suspension (see section V), we should recover Eq. (17) from Eq. (27) in the infinite dilution limit where $`R_{WS}`$ goes to infinity. We consequently expect the value $`𝒞=4`$ to be relevant for the situation of finite density of colloids with added salt. Searching for a unified description, we also test the possible validity of the choice $`𝒞=4`$ in the no salt situation. It is therefore instructive, as an illustration of the method and benchmark, to analyze the simple case of a charged plane confined in a WS cell, without added electrolyte. As recalled in Appendix B, the analytical solution of the non linear PB equation is known in such a geometry when counter-ions are the only micro-ions present, which allows to check the validity of our assumptions in the limiting case of finite concentration. Below, we compare these “exact” results to the predictions of our prescription.

The exact apparent potential, $`\varphi _S`$ is obtained using Eq. (B5) at $`x=0`$ for the plane: $`\varphi _S=\mathrm{cosh}(K_{_{\text{LPB}}}h)1`$. Our prescription imposes $`\varphi _S=4`$, yielding $`K_{_{\text{LPB}}}h=\mathrm{ArcCosh}(5)`$. The effective charge is obtained from Gauss theorem at the surface, i.e.  Eq. (B6) with $`\sigma `$ replaced by $`\sigma _{\text{eff}}`$. This leads to the final result of our prescription $`\sigma _{\text{sat}}=\sqrt{6}\mathrm{ArcCosh}(5)\sigma _c5.6\sigma _c`$ (where $`\sigma _c=1/\pi l_Bh`$), which should be compared to the exact result $`\sigma _{\text{sat}}5.06\sigma _c`$ \[see Eq. (B18) in appendix B\]. First it is striking to note that our prescription predicts the correct functional dependence of the effective charge in terms of the parameters of the system. Moreover the numerical prefactor in front of $`\sigma _c`$ is only within 10% of the “exact” value obtained in Eq. (B18), which is quite a satisfactory agreement.

However certainly the most interesting feature which comes out from the previous results is the fact that the apparent potential at contact, $`\varphi _S`$, obtained within the analytical resolution of the PB equation, does saturate to a constant value $`\varphi _S3.66`$ in the limit of very large bare charges: this value is very close to the value we prescribe, $`\varphi _S=4`$! This is a non trivial point, since the physical conditions in the present case are very different from the isolated plane case (previous section). We conclude that the analytic results available for a confined one-dimensional electric double-layer support our prescription. For a more refined analysis of the electrostatics of counter-ions between planar charged walls, going beyond PB, we refer to the work of Netz et al. .

In the remaining of this section, we further test our prescription against results for spherical and cylindrical macro-ions.

### B Spheroids

Here, the object is a charged spherical colloid (bare charge $`Ze`$, radius $`a`$) confined with its counter-ions in a concentric WS sphere (radius $`R_{WS}`$). The packing fraction is defined as $`\eta =(a/R_{WS})^3`$. PB equation is again linearized around the boundary of the WS cell, yielding Eq. (B4) which we recall here:

$$^2\varphi =K_{_{\text{LPB}}}^2\left(\varphi +1\right).$$
(28)
As for the planar case, the boundary conditions are $`\varphi (R_{WS})=0`$ (electroneutrality), $`\varphi _{_{\text{LPB}}}(R)=0`$ (because we impose by commodity the potential to vanish at the WS cell, see Appendix B). The solution $`\varphi _{_{\text{LPB}}}`$ thus reads:

$$\varphi _{_{\text{LPB}}}(r)=1+f_+\frac{e^{K_{_{\text{LPB}}}r}}{r}+f_{}\frac{e^{K_{_{\text{LPB}}}r}}{r}$$
(29)
with

$$f_\pm =\frac{K_{_{\text{LPB}}}R_{WS}\pm 1}{2K_{_{\text{LPB}}}}\mathrm{exp}(K_{_{\text{LPB}}}R_{WS}).$$
(30)
The charge $`Z_{\text{eff}}`$ of the colloid is obtained from the spatial derivative of $`\varphi _{_{\text{LPB}}}`$ at the colloid surface:

$$Z_{\text{eff}}=\frac{a}{\mathrm{}_B}\frac{1}{K_{_{\text{LPB}}}a}\left\{(1K_{_{\text{LPB}}}^2aR_{WS})\mathrm{sinh}[K_{_{\text{LPB}}}(R_{WS}a)]K_{_{\text{LPB}}}(R_{WS}a)\mathrm{cosh}[K_{_{\text{LPB}}}(Ri_{WS}a)]\right\}.$$
(31)
At this level the screening constant $`K_{_{\text{LPB}}}`$ is still unknown: it is fixed by our prescription which imposes the apparent potential of the colloid, such that $`\varphi _{_{\text{LPB}}}(r=a)=𝒞=4`$ with $`\varphi _{_{\text{LPB}}}(r)`$ given in Eq. (29). The effective charge, $`Z_{\text{sat}}`$, is eventually computed using Eq. (31). On the other hand $`K_{_{\text{PB}}}`$ is defined from the PB counter-ion density at WS boundary $`\rho ^{}(WS)`$:

$$K_{_{\text{PB}}}^2=4\pi \mathrm{}_B\rho ^{}(WS).$$
(32)
The equation for $`K_{_{\text{LPB}}}`$, $`\varphi _{_{\text{LPB}}}(r=a)=4`$, is solved numerically using a simple Newton procedure. Fig. 3 displays the corresponding $`Z_{\text{sat}}`$ as a function of $`\eta `$ together with the effective charge (again at saturation) found by solving *numerically* the full non linear PB equation, together with Alexander’s procedure. We recall that this procedure defines the effective charge entering LPB equation such that the solution of PB and LPB equations match up to the second derivative at the WS boundary. We emphasize that once PB equation has been solved numerically, no further numerical fitting procedure is required to match $`\varphi _{_{\text{LPB}}}`$ to $`\varphi _{_{\text{PB}}}`$ and compute the effective charge: the counter-ion density at WS boundary $`\rho ^{}(WS)`$ is known and $`K_{_{\text{PB}}}`$ follows from Eq. (32). Replacing $`K_{_{\text{LPB}}}`$ with this value in Eq. (31) then gives the “Alexander” $`Z_{\text{eff}}`$ (a similar remark holds with added salt, see below). We see again that our prescription works reasonably well.

### C Cylinders

Here we apply the previous procedure to an infinite cylinder (radius $`a`$, bare charge per unit length $`\lambda e`$) enclosed in a WS cylinder (same axis, radius $`R_{WS}`$). We define the packing fraction as $`\eta =(a/R_{WS})^2`$. This case is particularly interesting since the solution of the PB equation in the no-salt case is known from the work of Fuoss et al. and Alfrey et al. . This therefore provides another critical test of our prescription. We note that a similar approach has been followed by H. Löwen .

The calculation follows the same lines as for the previous spherical case. The solution of LPB equation (28) in the two dimensional case, with the usual boundary conditions and the choice $`\varphi _{_{\text{LPB}}}(R_{WS})=0`$ reads:

$$\varphi _{_{\text{LPB}}}(\rho )=1+K_{_{\text{LPB}}}R_{WS}\left\{\text{I}_1(K_{_{\text{LPB}}}R_{WS})\text{K}_0(K_{_{\text{LPB}}}\rho )+\text{K}_1(K_{_{\text{LPB}}}R_{WS})\text{I}_0(K_{_{\text{LPB}}}\rho )\right\},$$
(33)
where use was made of the identity $`x[I_0(x)K_1(x)+I_1(x)K_0(x)]=1`$. From the spatial derivative of $`\varphi _{_{\text{LPB}}}`$ at $`r=a`$ we deduce the effective line charge density $`\lambda _{\text{eff}}`$:

$$\lambda _{\text{eff}}\mathrm{}_B=\frac{1}{2}K_{_{\text{LPB}}}^2aR_{WS}\left\{\text{I}_1(K_{_{\text{LPB}}}R_{WS})\text{K}_1(K_{_{\text{LPB}}}a)\text{I}_1(K_{_{\text{LPB}}}a)\text{K}_1(K_{_{\text{LPB}}}R_{WS})\right\}.$$
(34)
If the above expression is evaluated replacing $`K_{_{\text{LPB}}}`$ by the exact $`K_{_{\text{PB}}}`$ following from (32) once the non-linear problem has been numerically solved, we obtain the original Alexander value (not necessarily at saturation, and without having to implement in practice a numerical fitting procedure). On the other hand, as in the spherical case, the screening constant $`K_{_{\text{LPB}}}`$ at saturation is obtained (approximately) by imposing the potential at the polyion’s surface: $`\varphi _{_{\text{LPB}}}(a)=𝒞=4`$ in the previous equation for $`\varphi _{_{\text{LPB}}}`$. Evaluation of Eq. (34) then gives the saturation value $`\lambda _{\text{sat}}`$.

This result is compared with the effective charge deduced by applying Alexander’s procedure to the analytical results of Fuoss et al. and Alfrey et al. in the large bare charge (saturation) limit : the corresponding “exact” value for the effective charge is chosen such that the solution of the linearized PB equation, Eq. (33), matches the solution of the non linear PB equation (Fuoss/Alfrey et al. solution) at the WS boundary up to the second derivative. The resulting effective charge is plotted on Fig. 4 together with the value of the effective charge obtained within our prescription. In Fig. 5, we compare the screening factor $`K_{_{\text{LPB}}}`$ obtained within our prescription to the “exact” value $`K_{_{\text{PB}}}`$ derived from the analytical solution of the PB equation and Eq. (32) (again in the limit of a large bare charge of the cylinder where the effective charge saturates). The agreement between both quantities is remarkable, even up to extremely high packing fractions (80% on Fig. 5).

Another interesting check concerns the apparent potential at the surface of the cylinder. Applying again Alexander’s procedure to the exact solution of Fuoss/Alfrey et al. , one obtains the LPB potential which matches the exact solution up to its third derivative at the WS cell boundary. The value of this potential at the surface $`\varphi _S^F`$ should be compared with the value we prescribe, i.e.  $`\varphi _S=4`$. The result is plotted on Fig. 6, showing again a good agreement except at low volume fraction, as expected (since as discussed in section III, our prescription is not expected to work in the very small $`\kappa a`$ limit).

Finally, we report an intriguing result: in the limit of vanishing density it can be shown analytically that $`K_{_{\text{PB}}}R_{WS}\sqrt{2}`$ . Using this result together with $`K_{_{\text{LPB}}}a0`$, we obtain from Eq. (34)

$$\underset{\eta 0}{lim}\lambda _{\text{sat}}=\frac{1}{\mathrm{}_B}\frac{\sqrt{2}}{2}\text{I}_1(\sqrt{2})0.6358\frac{e}{\mathrm{}_B}.$$
(35)
This asymptotic value is displayed in Fig. 4 with an arrow. We observe that this limit is approached (although very slowly) as $`\eta `$ decreases. Surprisingly, the result of Eq. (35) is very close to the exact expression (26) of Tracy and Widom  where the limit $`\kappa a0`$ is taken after that of infinite dilution. In principle, the limits of infinite dilution and of vanishing added salt have no reason to commute. The difference between the two $`\lambda _{\text{sat}}`$ quantities illustrates this point, with the surprise that the results are nevertheless very close numerically:

$`\underset{\text{no salt}}{lim}\underset{\mathrm{}\text{ dilution}}{lim}\lambda _{\text{sat}}0.6358{\displaystyle \frac{1}{\mathrm{}_B}}`$ (36)
$`\underset{\mathrm{}\text{ dilution}}{lim}\underset{\text{no salt}}{lim}\lambda _{\text{sat}}0.6366{\displaystyle \frac{1}{\mathrm{}_B}}.`$ (37)
## V Effective charge at finite concentration. The finite ionic strength case

We now turn to the case where salt is added to the colloidal suspension. More precisely, as already discussed in section II, we consider the semi grand canonical situation where the colloidal suspension is put in contact with a reservoir of salt, through a semi-permeable membrane (dialysis experiment). The concentration of mono-valent salt micro-ions in the reservoir $`\rho _0`$ fixes the chemical potential of the micro-ions in the suspension. However, due to the presence of the charged macro-ions, the salt concentration in the solution, $`\rho _s`$, differs from that in the reservoir $`\rho _0`$: this is the so-called “salt exclusion” or “Donnan effect” .

As in the previous section the effect of finite concentration is accounted for within PB cell theory (using a WS sphere of radius $`R_{WS})`$. Here again, we use the prescription Eq. (27) to predict the effective charge of the macro-ions. For this purpose, it is convenient to choose that the electrostatic potential $`\varphi `$ vanishes in the reservoir so that PB equation reads

$$^2\varphi =\kappa _{\text{res}}^2\mathrm{sinh}\varphi $$
(38)
where the screening factor $`\kappa _{\text{res}}`$ is defined in terms of the ionic strength of the reservoir: $`\kappa _{\text{res}}^2=8\pi \mathrm{}_BI_0`$.

Let us now consider the linearized (“LPB”) version of this equation. We again linearize around the value of the potential at the boundary of the WS cell, $`\varphi __\mathrm{\Sigma }=\varphi (R_{WS})`$, often referred to as the “Donnan potential”

$$^2\delta \varphi =K_{_{\text{LPB}}}^2(\delta \varphi +\gamma _0)$$
(39)
where we introduced $`\delta \varphi =\varphi \varphi __\mathrm{\Sigma }`$ and:

$`K_{_{\text{LPB}}}^2=\kappa _{\text{res}}^2\mathrm{cosh}[\varphi __\mathrm{\Sigma }]`$ (40)
$`\gamma _0=\mathrm{tanh}[\varphi __\mathrm{\Sigma }]=\sqrt{1\left({\displaystyle \frac{\kappa _{\text{res}}}{K_{_{\text{LPB}}}}}\right)^4}.`$ (41)
The second order differential equation (39) is solved invoking the two self consistent boundary conditions

$$\delta \varphi =0\text{and}\frac{\delta \varphi }{r}=0\text{for}r=R_{WS},$$
(42)
so that $`\delta \varphi `$ is known as a function of distance and depends parametrically on $`K_{_{\text{LPB}}}`$. We emphasize that $`K_{_{\text{LPB}}}`$ is still unknown at this point. It is computed as in section IV from our prescription on the reduced potential

$$\delta \varphi _S=\varphi _S\varphi __\mathrm{\Sigma }=4.$$
(43)
### A Spheroids

With the same notations as above, the appropriate solution of LPB equation (39) is

$$\delta \varphi _{_{\text{LPB}}}(r)=\gamma _0\left[1+f_+\frac{e^{K_{_{\text{LPB}}}r}}{r}+f_{}\frac{e^{K_{_{\text{LPB}}}r}}{r}\right]$$
(44)
where the functions $`f_\pm `$ are defined in Eq. (30). Note that expression (29) is recovered by taking the formal limit $`\kappa _{\text{res}}=0`$ in the previous equation.

Our prescription allows to compute $`K_{_{\text{LPB}}}`$ at saturation, such that $`\delta \mathrm{\Phi }(a)=4`$, without any reference to the solution of the non linear PB problem. This equation is solved numerically using a Newton procedure. Once $`K_{_{\text{LPB}}}`$ is known, the effective charge follows from the gradient of $`\delta \varphi (r)`$ in Eq. (44) taken at $`r=a`$ (it may also be computed by integrating the corresponding LPB charge density over the volume accessible to the micro-ions, i.e. $`arR_{WS}`$)

$$Z_{\text{sat}}=\gamma _0\frac{a}{\mathrm{}_B}\frac{1}{K_{_{\text{LPB}}}a}\left\{(K_{_{\text{LPB}}}^2aR_{WS}1)\mathrm{sinh}[K_{_{\text{LPB}}}(R_{WS}a)]+K_{_{\text{LPB}}}(Ri_{WS}a)\mathrm{cosh}[K_{_{\text{LPB}}}(Ri_{WS}a)]\right\}$$
(45)
with $`\gamma _0=\sqrt{1(\kappa _{\text{res}}/K_{_{\text{LPB}}})^4}`$. Again, our prescription $`\delta \varphi _S=\varphi _S\varphi __\mathrm{\Sigma }=4`$ provides a value for $`K_{_{\text{LPB}}}`$ which is an approximation for the exact $`K_{_{\text{PB}}}`$ at saturation, related to microions densities at the WS boundary through the expected Debye-like form

$$K_{_{\text{PB}}}^2=\mathrm{\hspace{0.17em}4}\pi \mathrm{}_B\left[\rho ^+(WS)+\rho ^{}(WS)\right].$$
(46)
If Eq. (45) is evaluated with the exact $`K_{_{\text{PB}}}`$, Alexander’s original effective charge follows (hence without having to implement any numerical fitting procedure). We also emphasize that as in the previous sections, the right hand side of Eq. (45) provides the effective $`Z_{\text{eff}}`$ à la Alexander (i.e not necessarily at saturation), once evaluated with the correct $`K_{_{\text{PB}}}`$ (deduced from the numerical solution of the non-linear problem).

The results for the effective charge at saturation $`Z_{\text{sat}}`$ as a function of volume fraction are displayed on Fig. 7 for $`\kappa _{\text{res}}a=2.6`$. As in the previous sections, we compare this result with its Alexander’s counterpart at saturation. Our predictions are seen to be compatible with those obtained in the PB cell model.

From the numerical solution of the PB equation, it is possible to extract the apparent surface potential, $`\delta \varphi _S=\varphi (r=a)\varphi (R_{WS})`$ (in the latter expression $`\varphi `$ is defined as the solution of the LPB equation matching the full -numerical- PB equation up to second derivative at the WS cell boundary). By construction, this potential may be obtained inserting the numerically obtained $`K_{_{\text{PB}}}\kappa _{\text{res}}\mathrm{cosh}^{1/2}(\varphi __\mathrm{\Sigma })`$ into (44). This apparent potential should be compared against our prescription $`\delta \varphi =4`$. The corresponding result is shown on Fig. 8. We observe that $`\delta \varphi _S`$ indeed saturates to a value close to $`4`$. The inset shows $`K_{_{\text{LPB}}}/K_{_{\text{PB}}}`$ versus $`\eta `$, where $`K_{_{\text{PB}}}`$ is the “exact” screening length for the LPB equation at saturation, obtained numerically; $`K_{_{\text{LPB}}}`$ is the same quantity estimated from our prescription. We observe that although for small packing fractions $`\delta \varphi _S`$ slightly departs from our approximation $`𝒞=4`$, the estimated $`K_{_{\text{LPB}}}`$ is still remarkably close to the exact one.

Independently of our prescription, we finally test the relevance of Alexander’s procedure  in the following way. $`Z_{\text{sat}}`$ has been obtained above from the matching of a generic LPB potential to the numerical PB one at $`r_{\text{match}}=R_{WS}`$. It is also possible to implement the matching at a different location inside the cell, and we denote $`Z_{\text{sat}}(r_{\text{match}})`$ the associated effective charge, at saturation. This quantity, normalized by the “usual” one $`Z_{\text{sat}}(R_{WS})`$ is displayed in Fig. 9. For the packing fraction of 5% considered, $`r_{\text{match}}/R_{WS}`$ is bounded below by $`a/R_{WS}0.37`$, and $`Z_{\text{sat}}(R_{WS})16.7a/\mathrm{}_B`$, see Fig. 7. We observe that $`Z_{\text{sat}}`$ is relatively insensitive to $`r_{\text{match}}`$ for $`0.6R_{WS}r_{\text{match}}R_{WS}`$.

### B Rod-like polyions

Using the same notations as in section IV, the appropriate solution of the LPB equation in cylindrical geometry reads

$$\delta \varphi _{_{\text{LPB}}}(\rho )=\gamma _0\left\{K_{_{\text{LPB}}}R_{WS}\left[\text{I}_1(K_{_{\text{LPB}}}R_{WS})\text{K}_0(K_{_{\text{LPB}}}\rho )+\text{K}_1(K_{_{\text{LPB}}}R_{WS})\text{I}_0(K_{_{\text{LPB}}}\rho )\right]1\right\}.$$
(47)
with $`\gamma _0=\sqrt{1(\kappa _{\text{res}}/K_{_{\text{LPB}}})^4}`$. Again, $`K_{_{\text{LPB}}}`$ is obtained as the solution of the equation $`\delta \varphi _{_{\text{LPB}}}(\rho =a)=4`$. Once this equation is solved, the saturation value of the effective charge, $`\lambda _{\text{eff}}`$, follows from the spatial derivative of the potential $`\delta \varphi _{_{\text{LPB}}}`$ at the rod surface:

$$\lambda _{\text{eff}}=\frac{1}{2\mathrm{}_B}K_{_{\text{LPB}}}^2aR_{WS}\gamma _0\left\{\text{I}_1(K_{_{\text{LPB}}}Ri_{WS})\text{K}_1(K_{_{\text{LPB}}}a)\text{I}_1(K_{_{\text{LPB}}}a)\text{K}_1(K_{_{\text{LPB}}}Ri_{WS})\right\}.$$
(48)
As in the previous sections, Eq. (48) gives analytically the relation between the effective charge à la Alexander et al. and micro-ions densities at the WS boundary. As such, it applies for any value of the bare charge $`\lambda `$, and in particular, for $`\lambda 0`$, $`K_{_{\text{LPB}}}`$ is such that $`\lambda _{\text{eff}}/\lambda 1`$. A similar remark applies for Eqs. (31), (34) and (45). If we choose for $`K_{_{\text{LPB}}}`$ the “exact” $`K_{_{\text{PB}}}`$ value, we recover the “exact” cell model (Alexander) effective charges. However, the quantity $`K_{_{\text{LPB}}}`$ solution of $`\delta \varphi _{_{\text{LPB}}}(\rho =a)=4`$ is supposedly the inverse screening length at saturation and therefore provides an approximation of $`\lambda _{\text{sat}}`$ once inserted into (48).

The corresponding results for $`\lambda _{\text{sat}}`$ as a function of volume fraction are displayed in Fig. 10 for $`\kappa _{\text{res}}a=3`$. As in the previous sections, we compare this result with its counterpart obtained from the numerical solution of PB theory together with Alexander’s procedure for the effective charge in the saturation limit. The agreement with the numerical results of the full non linear PB equation is seen to be satisfactory.

## VI Confrontation to experimental and numerical results

In the previous sections, we have tested our results for the effective charges against the numerical solutions of PB theory. However, the effective charge is a difficult quantity to measure directly in an experiment (see however the work reported in  confirming the scaling $`Z_{\text{sat}}a/\mathrm{}_B`$ for low ionic strength suspensions of spherical latex colloids). In order to assess the experimental relevance of the above ideas, we now turn to the computation of osmotic properties for spherical and rod-like macro-ions, easily accessible both experimentally and within our approach. In the case of spherical colloids, we start by considering the phase behaviour of the suspension as a function of added salt.

### A Crystallization of charged spheres

The phase diagram of charged spherical colloids has been widely explored experimentally, in particular by Monovoukas and Gast . In this work, the macro-ions were charged polystyrene spheres, with radius $`a660`$Å. The authors moreover compared their experimental phase diagram to that computed for particles interacting through a Yukawa potential (1) (the Yukawa phase diagram has indeed been investigated extensively by numerical simulations ). However such a comparison experiment/theory requires an ad-hoc choice for the effective charge $`Z_{\text{eff}}`$ \[prefactor of Eq. (1)\]. The authors found that a reasonable agreement with the numerical results was obtained for a specific choice of the effective charge, $`Z_{\text{sat}}=880`$ (although they reported conductimetry experiments indicating a macro-ion charge around $`1200`$).

We focus in the following on the melting line of the phase diagram obtained in . We use here our predictions for the effective charges at saturation: we do not need to know the bare charge of the polystyrene spheres, as this quantity is presumably much larger than the corresponding saturation plateau of $`Z_{\text{eff}}`$, which means, within the PB picture, that $`Z_{\text{eff}}Z_{\text{sat}}`$. Once $`Z_{\text{sat}}`$ (and the corresponding screening constant $`K_{_{\text{LPB}}}`$, see previous section) is known for a given density and ionic strength, it is possible to insert it into the computed generic phase diagram of Yukawa systems  to obtain the corresponding stable phase. We extract in particular the melting line from these numerical results: we prefer to use these numerical results for the phase diagram (instead of performing a full theoretical analysis) since our main focus remains to check the relevance of our predictions for the effective charges. This requires a “reliable” description for the melting line, which numerical simulations provide once the potential is given.

We emphasize that at this level, the only parameter entering our description is the diameter of the beads, which is measured independently. Accordingly, there is no adjustable parameter in our equations and the resulting phase diagram is strongly constrained. The results for the melting line using our prescription for the effective charge are confronted to the experimental data in Fig. 11. We also plot the result for the melting line for an ad hoc constant effective charge, $`Z_{\text{sat}}=880`$, as was proposed in Ref. . The observed agreement supports the pertinence of our prescription for $`Z_{\text{sat}}`$ which reproduces the experimental phase diagram. In our case, the effective charge does vary between 500 and 2000 along the melting line, depending on ionic strength and density. This could explain that the conductimetry measurements performed independently by Monovoukas and Gast (although at an unspecified ionic strength) yield another value for the effective charge of the spheres ($`Z1200`$ as quoted above).

### B Osmotic pressure of a suspension of spherical colloids

In the PB cell model, the osmotic pressure in the solution is related to the densities of micro-ions at the WS cell boundary :

$$\mathrm{\Pi }_{\text{osm}}=k_BT\left[\rho ^+(R_{WS})+\rho ^{}(R_{WS})2\rho _0\right],$$
(49)
where we have subtracted the ionic contribution from the reservoir (of salt density $`\rho _0=I_0`$). This is because the electric field vanishes at the WS cell and there is no contribution from the electrostatic pressure at $`r=R_{WS}`$. Using Eq. (46), Eq. (49) may be recast into

$$\mathrm{\Pi }_{\text{osm}}=\frac{k_BT}{4\pi \mathrm{}_B}[K_{_{\text{PB}}}^2(\rho ,I_0)\kappa _{\text{res}}^2],$$
(50)
where $`\kappa _{\text{res}}`$ is the screening constant defined in terms of the ionic strength in the reservoir. Our prescription is supposed to give an excellent approximate of the non-linear $`K_{_{\text{PB}}}`$ through $`K_{_{\text{LPB}}}`$, and readily allows an estimation of the osmotic pressure. Figure 12 shows the accuracy of the estimate, with or without added electrolyte.

The comparison of our predictions at saturation to the experimental results reported by Reus et al.  is also satisfactory, see Fig. 13. It was already pointed out in  that PB cell theory reproduced well the experimental data. The agreement observed in Fig. 13 however illustrates the relevance of the PB saturation picture –well captured by our approach– at high polyion/micro-ion electrostatic coupling (see the discussion in section VII).

### C Osmotic properties of rod-like polyions

Expression (50) is also valid in cylindrical geometry, and we show in Fig. 14 the comparison prescription versus non-linear PB osmotic pressure. We draw a similar conclusion as for spherical polyions concerning the accuracy of our approximation.

For completeness, we compare in what follows our estimate for the osmotic pressure to the experimental results on B-DNA solutions reported in . In this work, the authors measured the osmotic coefficient $`\varphi =\mathrm{\Pi }_{\text{osm}}/\mathrm{\Pi }_c`$, defined as the ratio between the osmotic pressure $`\mathrm{\Pi }_{\text{osm}}`$ to the pressure $`\mathrm{\Pi }_c`$ of releasable counter-ions having bare density $`c_c`$ ($`\mathrm{\Pi }_c=k_BTc_c`$) against the concentration of B-DNA, a rigid cylindrical polyelectrolyte. A related PB cell analysis may be found in  while a more thorough investigation has been performed in .

Within the WS model, B-DNA macro-ions are confined into cylindrical cells, which radius $`R_{WS}`$ is related to the bare concentration of DNA counter-ions as $`c_c=(\mathrm{}_{DNA}\pi R_{WS}^2)^1`$, with $`\mathrm{}_{DNA}=1.7`$Å the distance between charges along DNA. Note that as in the previous section dealing with charged spheres, there is no adjustable parameter in our description since the radius of the DNA and the bare charge (only used to normalize the osmotic pressure to $`\mathrm{\Pi }_c`$) are known from independent measurements. In Fig. 15, the corresponding results for the osmotic coefficient are confronted against the experimental data of Refs.  for various ionic strengths, showing again a good quantitative agreement. As in Ref. , we report the prediction of classical Oosawa-Manning condensation theory (see e.g. ), for which the osmotic coefficient is constant \[$`\varphi =\mathrm{}_{DNA}/(2\mathrm{}_B)`$\] at complete variance with the experiments. In view of the results reported in Fig. 14, the disagreement at small $`c_c`$ may be attributed to the (relative) failure of PB theory, and not to a weakness of our prescription that should be judged with respect to non-linear PB.

## VII Discussion - Validity of the approach

Our analysis was carried out at the level of Poisson-Boltzmann theory, which is mean-field like. More refined approaches such as the salt free Monte Carlo simulations of Groot  for the cell model within the primitive model  have shown a non-monotonic behaviour of $`Z_{\text{eff}}`$ upon increasing $`Z`$ for spheres: after the linear regime where $`Z_{\text{eff}}Z`$, $`Z_{\text{eff}}`$ reaches a maximum for a value $`Z_{\text{bare}}^{}`$ and then decreases. When the radius $`a`$ of the charged spheres is much larger than Bjerrum length $`\mathrm{}_B`$, this maximum is surrounded by a large plateau in excellent agreement with the PB saturation value $`Z_{\text{sat}}`$ . PB theory appears to become exact for $`\mathrm{}_B/a0`$ . Given that, $`Z_{\text{bare}}^{}`$ scales like $`(a/\mathrm{}_B)^2`$ and therefore becomes quickly large when the colloid size is increased , PB theory is successful in the colloidal limit of large $`a`$. We recall that this is precisely the limit where our predictions for the effective charge at saturation $`Z_{\text{sat}}`$ are reliable (the condition $`a\kappa ^1`$ should a priori be satisfied even if we have shown above that our predictions remain fairly accurate down to $`\kappa a`$ of order 1). More generally, the results of Groot  show that the effective charge $`Z_{\text{eff}}`$ from Monte Carlo simulations within the primitive model for arbitrary $`a/\mathrm{}_B`$ are smaller than the quantity $`Z_{\text{sat}}`$ of PB theory. This is a general feature that neglect of ionic correlation (as in PB) leads to a underestimated screening of the macro-ion by the micro-ions, and thus to overestimated effective charges (see e.g.  in cylindrical geometry). Our approach thus provides a useful upper limit for a realistic $`Z_{\text{eff}}`$.

A related comment in favor of the validity of PB picture with a saturation plateau for $`Z_{\text{eff}}`$ comes from the work of Cornu and Jancovici . For the two dimensional two-component Coulomb gas bounded by a hard wall of surface charge $`\sigma `$, these authors performed an exact calculation at the inverse reduced temperature $`e^2/(kT)=2`$ showing that the effective surface charge of the wall saturates to a plateau value when $`\sigma `$ diverges.

Generally speaking, in an 1:1 electrolyte, PB theory seems to be a reasonable approximation , all the better that the size of the macro-ion is larger than $`\mathrm{}_B`$; the notion of charge renormalization then encaptures the main effects of the non-linear PB theory, and is consistent with experimental data on dilute bulk solution  (see also the experimental work cited in section VI). For micro-ions of higher valences (di- or tri-valent), strong ionic correlations rule out PB-like approaches, as shown by recent computer simulations of the primitive model . As a consequence, the results presented here should a priori not be used in the interpretation of experiments involving multivalent salts or counter-ions. For a discussion concerning the effects of multivalent counter-ions, we refer to the review by Bhuiyan, Vlachy and Outhwaite .

## VIII Conclusion

The notion of effective charge is widely used in the fields of colloidal suspensions. It allows in practice to describe the phase behavior of (highly) charged macro-ions staying at the level of linearized Poisson-Boltzmann equations, where the macro-ions are supposed to interact through Yukawa-like pair potentials. However, no general analytical description of this renormalization process is available and the effective charge is usually left as a free parameter, adjusted to fit experimental (or numerical) data. Physically the charge renormalization process results from the strong coupling of the micro-ions in the vicinity of the highly charged colloidal particle. At the level of Poisson-Boltzmann theory, the effective charge saturates to a finite value in the limit where the bare charge becomes large. We recall that omission of the non-linearities of PB theory –correctly accounted for by the notion of effective charge– may lead to unphysical results (see e.g. ).

In the present paper, we have put forward a simple method to estimate the effective charge of highly charged colloidal objects either analytically, or through the resolution of a simple equation obtained within linearized Poisson-Boltzmann approximation. This approach (mostly suited to describe the colloidal limit $`\kappa a1`$) amounts to consider the highly charged colloids as objects with constant electrostatic potential $`4kT/e`$, independently of shape and physico-chemical parameters (size, added 1:1 electrolyte…). This result relies on the physical picture that the electrostatic energy $`eV_0`$ of the strongly coupled micro-ions (i.e.  micro-ions in the vicinity of the highly charged macro-ion) does balance their thermal (entropic) energy $`k_BT`$, resulting in a constant effective surface potential for the “dressed” macro-ion. We have successfully tested this approach against a) the geometry of the solid particle, b) the confinement (finite concentration situations), c) the presence of added salt, d) exact and approximate solutions of the full non-linear PB equations e) direct experimental measurements of the effective charge found in the literature. From these different checks, we conclude that our prescription appears to contain the key ingredients involved in charge renormalization.

An important point is that the effective charge is not constant and depends explicitly on the physical conditions of the experiment, through ionic strength, density, etc …. The effect is quite obvious in the small dilution limit, where we found that the (saturated) effective charge is an increasing function of $`\kappa `$ (for $`\kappa a>1`$, which stems from the reduction of the attraction between the counter-ions and the colloid. It pertains for finite concentration and the effective charge increases with the ionic strength in the suspension. Addition of salt consequently brings two antagonist effects on the effective Coulombic interaction between macro-ions: the range of the interaction decreases due to screening, while the amplitude increases due to the effective charge. The competition between these two effects might be a key point in the understanding of these systems. It appears therefore interesting to reconsider the phase stability of macro-ion suspension in light of these results (see also  and more recently ).

Eventually it would be desirable to extend our approach to the case of finite size colloidal particles, such as rods with finite length or disks . Accordingly, edge effects should show up at the level of our prescription and result in an effective charge distribution along the macro-ion, due to the constant potential prescription on the object. Work along these lines is in progress.

Acknowledgments: We would like to thank J.P. Hansen, H. Löwen, H.H. von Grünberg, M. Deserno, C. Holmand, J.F. Joanny for useful discussions.

## A Analytical solution of PB equation for an isolated plane in an electrolyte

Here, we recall the analytical solution of PB equation for an isolated plane of bare surface charge $`\sigma e`$ immersed in an electrolyte of bulk ionic strength $`I_0`$. In this case, the solution of equation (6) reads :

$$\varphi _{_{\text{PB}}}(z)=2\mathrm{ln}\frac{1+\gamma e^{\kappa z}}{1\gamma e^{\kappa z}}$$
(A1)
where $`\gamma =\sqrt{x^2+1}x`$, $`\kappa ^2=8\pi \mathrm{}_BI_0`$ and $`x=\kappa \lambda _{GC}`$, with the Gouy-Chapman length defined as

$$\lambda _{GC}=\frac{1}{2\pi l_B\sigma }.$$
(A2)
Far from the charged surface, say $`z>2\kappa ^1`$, the solution of PB equation reduces to

$$\varphi _{_{\text{PB}}}(z)\varphi _Se^{\kappa z}$$
(A3)
with $`\varphi _S=4\gamma `$. The potential $`\varphi _S`$ can be interpreted as the apparent reduced potential extrapolated at contact. In the following we shall simply refer to $`\varphi _S`$ as the apparent potential.

As expected, this asymptotic expression for the reduced potential $`\varphi _{_{\text{PB}}}`$ in Eq. (A3) precisely matches the solution $`\varphi _{_{\text{LPB}}}`$ of the linearized PB (LPB) equation:

$$^2\varphi _{_{\text{LPB}}}=\kappa ^2\varphi _{_{\text{LPB}}}$$
(A4)
but with the fixed charge boundary condition on the plane replaced by an effective fixed surface potential boundary condition $`\varphi _{_{\text{LPB}}}(z=0)=\varphi _S=4\gamma `$. The effective charge density is then computed using Gauss theorem at the surface, yielding

$$\sigma _{\text{eff}}=\frac{\gamma \kappa }{\pi l_B}.$$
(A5)
In doing so, we have replaced the initial non linear PB equation with fixed charge boundary condition by the linear LPB equation with fixed surface potential.

Now at fixed $`\kappa `$ (i.e. constant ionic strength), we progressively increase the bare surface charge $`\sigma `$. Accordingly $`\kappa \lambda _{GC}0`$ and the parameter $`\gamma `$ goes to 1. From Eq. (A5), we obtain that the effective charge and the apparent potential $`\varphi _S`$ have a simple behaviour depending on the comparison of $`\sigma `$ with $`\sigma _{\text{sat}}`$ defined as

$$\sigma _{\text{sat}}=\frac{\kappa }{\pi l_B}.$$
(A6)
Indeed

$`\sigma \sigma _{\text{sat}}`$ $`\sigma _{\text{eff}}\sigma `$ (A8)
$`\varphi _S4\sigma /\sigma _{\text{sat}}`$
$`\sigma \sigma _{\text{sat}}`$ $`\sigma _{\text{eff}}\sigma _{\text{sat}}`$ (A10)
$`\varphi _S4`$
The important point is that in the large bare charge limit, $`\sigma \sigma _{\text{sat}}`$, the effective charge $`\sigma _{\text{eff}}`$ saturates to a value $`\sigma _{\text{sat}}`$ independent of the bare one, $`\sigma `$. In this limit, the apparent potential also saturate to a constant value, $`\varphi _S=4`$.

## B Analytical solution of PB equation for a confined plane without added salt

An infinite plane (bare surface charge density $`\sigma e`$) is placed in the middle of a Wigner-Seitz slab of width $`2h`$. The origin of coordinates $`x=0`$ is chosen at the location of the plane such that the volume available to the counter-ions is $`hxh`$. For symmetry reasons, it is enough to solve the problem for $`x>0`$. The electrostatic potential $`\varphi `$ obeys PB equation (4), supplemented with Neumann boundary conditions: $`\varphi (h)=0`$, corresponding to the electroneutrality condition; $`\varphi (0)=2\pi \mathrm{}_B\sigma `$ imposing the charge on the plane. Without loss of generality, we choose the origin of potential such that $`\varphi (h)=0`$; the analytical solution of PB equation then reads

$$\varphi _{_{\text{PB}}}(x)=\mathrm{log}\left[\mathrm{cos}^2\left(\frac{\left(|x|h\right)}{\sqrt{2}K_{_{\text{PB}}}^1}\right)\right],$$
(B1)
where $`K_{_{\text{PB}}}(\sigma )`$ is such that

$$\frac{hK_{_{\text{PB}}}}{\sqrt{2}}\mathrm{tan}\left(\frac{hK_{_{\text{PB}}}}{\sqrt{2}}\right)=\pi \mathrm{}_B\sigma h.$$
(B2)
The inverse screening length $`K_{_{\text{PB}}}`$ is related to the density of counter-ions at the WS boundary $`\rho ^{}(h)`$ through the following expression, reminiscent of the standard definition of the Debye length

$$K_{_{\text{PB}}}^2=\mathrm{\hspace{0.17em}4}\pi \mathrm{}_B\rho ^{}(h).$$
(B3)
Now we consider the corresponding LPB equation. More precisely, we linearize Eq. (4) around $`x=h`$ (i.e. the edge of the slab). Since we have chosen $`\varphi _{_{\text{PB}}}(h)=0`$, we impose $`\varphi _{_{\text{LPB}}}`$ to vanish at $`x=h`$. The resulting equation reads

$$^2\varphi =K_{_{\text{LPB}}}^2\left(\varphi +1\right)$$
(B4)
where we have introduced $`K_{_{\text{LPB}}}`$, an “apparent” local Debye screening factor for the linearized PB equation. As for the previous PB equation in the no salt case, $`K_{_{\text{LPB}}}`$ is not known a priori but results from the electroneutrality condition. Indeed, solving Eq. (B4) with the appropriate boundary conditions \[$`\varphi (h)=0`$, $`\varphi (0)=4\pi \mathrm{}_B\left(\sigma /2\right)`$\] yields

$$\varphi _{_{\text{LPB}}}(x)=\mathrm{cosh}\left[K_{_{\text{LPB}}}\left(xh\right)\right]1,$$
(B5)
with $`K_{_{\text{LPB}}}(\sigma )`$ such that

$$hK_{_{\text{LPB}}}\mathrm{sinh}\left[K_{_{\text{LPB}}}h\right]=2\pi \mathrm{}_B\sigma h$$
(B6)
Note that comparing Eqs. (B2) and (B6), we see that $`K_{_{\text{LPB}}}(\sigma )K_{_{\text{PB}}}(\sigma )`$. It is however crucial to remember that the LPB solution should not be used with the bare charge $`\sigma `$ to describe the correct behaviour of $`\varphi _{_{\text{PB}}}`$ in the vicinity of $`x=h`$.

Next, we implement the procedure proposed by Alexander to find the effective charge in confined situations . The effective charge density is accordingly the value of $`\sigma `$ in the linearized PB equation such that $`\varphi _{_{\text{PB}}}(x)`$ and $`\varphi _{_{\text{LPB}}}(x)`$ match up to the second derivative at $`\mathrm{\Sigma }`$, the boundary of the WS cell . This condition is equivalent to set

$$K_{_{\text{LPB}}}\left(\sigma _{\text{eff}}\right)=K_{_{\text{PB}}}(\sigma ).$$
(B7)
Note that in general, whenever the solution of the non-linear PB problem is known, the effective charge $`\sigma _{\text{eff}}`$ can be directly estimated with Eq. (B7) (this is of course quite academic to obtain in this case an effective charge since the full solution for the potential is known; the notion of effective charge is mostly useful in geometries where no analytical solution of the PB equation is known). Note also that whenever Eq. (B7) is verified, the third, fourth and fith derivative of the linear and non-linear solutions also match at $`\mathrm{\Sigma }`$.

One deduces eventually the “exact” effective charge from Eq. (B7) for the plane case (by “exact” we mean that the effective charge is obtained from the analytical solution of PB equation, in contrast to our prescription):

$$\sigma _{\text{eff}}=\frac{K_{_{\text{PB}}}(\sigma )\mathrm{sinh}\left[K_{_{\text{PB}}}(\sigma )h\right]}{2\pi \mathrm{}_B}.$$
(B8)
The apparent potential $`\varphi _S`$ is also obtained as

$$\varphi _S=\varphi _{_{\text{LPB}}}(0)=\mathrm{cosh}\left[K_{_{\text{PB}}}(\sigma )h\right]1.$$
(B9)
From Eq. (B2), we define a critical value for the charge density

$$\sigma _c=\frac{1}{\pi l_Bh}$$
(B10)
and we find the asymptotic behaviors

$`\sigma `$ $``$ $`\sigma _c\{\begin{array}{c}hK_{_{\text{PB}}}(2\sigma /\sigma _c)^{1/2}\hfill \\ \sigma _{\text{eff}}\sigma \hfill \\ \varphi _S2\sigma /\sigma _c\hfill \end{array}`$ (B14)
$`\sigma `$ $``$ $`\sigma __c\{\begin{array}{c}hK_{_{\text{PB}}}\pi /\sqrt{2}\hfill \\ \sigma _{\text{eff}}\sigma _{\text{sat}}=\frac{\pi }{2\sqrt{2}}\mathrm{sinh}\left[\frac{\pi }{\sqrt{2}}\right]\sigma _c5.06\sigma _c\hfill \\ \varphi _S\mathrm{cosh}\left[\frac{\pi }{\sqrt{2}}\right]13.66\hfill \end{array}`$ (B18)
As in the infinite dilution limit, one obtains that the effective charge $`\sigma _{\text{eff}}`$ coincides with the bare one $`\sigma `$ for small $`\sigma `$, and saturates to a finite value when $`\sigma \mathrm{}`$. However both $`\sigma _c`$ and the saturation value for the effective charge at finite concentration differ from the $`\sigma _{\text{sat}}`$ of infinite dilution \[Eq. (A6)\]. We also note that strictly speaking, the limits of infinite dilution and of vanishing added salt do not commute: if the limit of vanishing salt is taken first (situation investigated in this appendix), before $`h\mathrm{}`$, we obtain $`\varphi _S^{\text{sat}}=\mathrm{cosh}\left[\pi /\sqrt{2}\right]1`$, whereas reverting the order corresponds to the planar situation of Appendix A with $`\kappa 0`$, and there, we have $`\varphi _S^{\text{sat}}=4`$. In both cases however, the effective charge at saturation vanishes.


text:
# Self–dual Lorentzian wormholes in n–dimensional Einstein gravity

## I Introduction

During the past two decades, considerable interest has grown in the field of wormhole physics, which has rapidly grown into an active area of research. Two separate directions emerged: one relating to Euclidean signature metrics and the other concerned with Lorentzian ones.

From the point of view of the Euclidean path integral formulation of quantum gravity ColemanColeman , and Giddings and Ströminger Strominger , among others, have shown that the effect of wormholes is to modify the low energy coupling constant, and to provide probability distributions for them.

On the purely gravitational side, the interest has been focused on Lorentzian wormholes. The interest in this area was especially stimulated by the pioneering works of Morris, Thorne and Yurtsever Morris ; Morris1 , where static, spherically symmetric Lorentzian wormholes were defined and considered to be an exciting possibility for constructing time machine models with these exotic objects, for backward time travel (see also Novikov ).

Most of the efforts are directed to study static configurations that must have a number of specific properties in order to be traversable. The most striking of these properties is the violation of energy conditions. This implies that the matter that generates the wormholes is exotic Morris ; Morris1 ; Visser , which means that its energy density is negative, as seen by static observers. These wormholes have no horizons and thus allow two–way passage through them.

On the other hand, many theories of unification (e.g. superstring theories, M–theory) require extra spatial dimensions to be consistent. Until today a number of important solutions of Einstein equations in higher dimensions have been obtained and studied, and they have led to important generalizations and wider understanding of gravitational fields. For example, Myers and Perry Myers  have found the n–dimensional versions of the Schwarzschild, Reissner–Nordstrom and Kerr solutions, and have discussed the associated singularities, horizons and topological properties. Dianyan Dianyan  has considered the n–dimensional Schwarzschild–de Sitter and Reissner–Nordstrom–de Sitter spacetimes.

An exact general solution of Einstein equations for spherically symmetric perfect fluids in higher dimensions was found by Krori, Borgohain and Das Krori . Ponce de Leon and Cruz Norman  discuss the question of how the number of dimensions of space–time influences the equilibrium configurations of stars.

Higher dimensional wormholes have also been considered by several authors. Euclidean wormholes have been studied by Gonzales–Diaz and by Jianjun and Sicong Gonzales  for example. The Lorentzian ones have been studied in the context of the n–dimensional Einstein–Gauss–Bonnet theory of gravitation Biplab . Evolving higher dimensional wormholes have been studied by Kar and Sahdev and by A. DeBenedictis and Das Sayan ; DeBenedictis .

It is the purpose of the present paper to obtain, following the prescription provided by Dadhich, Kar, Mukherjee and Visser Dadhich , a family of spherically symmetric, static and self–dual Lorentzian wormholes in n–dimensional Einstein Gravity.

The outline of the present paper is as follows: In Sec. II we briefly review some important aspects of 4–dimensional Lorentzian wormholes and give the definition of self–dual wormholes developed in Dadhich . In Sec. III a new class of metrics is presented which represent self–dual Lorentzian wormholes in n–dimensional Einstein gravity. Their properties are studied. We use the metric signature ($`+++`$) and set $`c=1`$.

## II 4–dimensional Lorentzian wormholes

### II.1 Characterization of Lorentzian wormhole

The metric ansatz of Morris and Thorne Morris  for the spacetime which describes a static Lorentzian wormhole is given by

$`ds^2=e^{2\varphi (r)}dt^2+{\displaystyle \frac{dr^2}{1\frac{b(r)}{r}}}+r^2(d\theta ^2+sin^2\theta d\phi ^2),`$ (1)
where the functions $`\varphi (r)`$ and $`b(r)`$ are referred to as redshift function and shape function respectively.

Morris and Thorne have discussed in detail the general constraints on the functions $`b(r)`$ and $`\varphi (r)`$ which make a wormhole Morris :

Constraint 1: A no–horizon condition, i.e. $`e^{\varphi (r)}`$ is finite throughout the space–time in order to ensure the absence of horizons and singularities.

Constraint 2: Minimum value of the r–coordinate, i.e. at the throat of the wormhole $`r=b(r)=b_0`$, $`b_0`$ being the minimum value of $`r`$.

Constraint 3: Finiteness of the proper radial distance, i.e.

$`{\displaystyle \frac{b(r)}{r}}1,`$ (2)
(for $`rb_0`$) throughout the space–time. This is required in order to ensure the finiteness of the proper radial distance $`l(r)`$ defined by

$`l(r)=\pm {\displaystyle _{b_0}^r}{\displaystyle \frac{dr}{\sqrt{1b(r)/r}}}.`$ (3)
The $`\pm `$ signs refer to the two asymptotically flat regions which are connected by the wormhole. The equality sign in (2) holds only at the throat.

Constraint 4: Asymptotic flatness condition, i.e. as $`l\pm \mathrm{}`$ (or equivalently, $`r\mathrm{}`$) then $`b(r)/r0`$.

Notice that these constraints provide a minimum set of conditions which lead, through an analysis of the embedding of the spacelike slice of (1) in a Euclidean space, to a geometry featuring two asymptotically flat regions connected by a bridge Dadhich .

In this paper we are not including considerations about the traversability constraints discussed by Morris and Thorne Morris .

### II.2 Self–dual Lorentzian wormholes

In order to construct a wormhole, one has to specify or determine the red–shift function $`\varphi (r)`$ and the shape function $`b(r)`$. In general one of them is chosen by fiat and the other is determined by implementing some physical condition. In this paper we shall use the definition of self–dual wormholes developed in Dadhich  and use it to obtain the n–dimensional self–dual version. The authors of Ref. Dadhich  have proposed the following equation as the equation for wormhole:

$`\rho =\rho _t=0,`$ (4)
where $`\rho =T_{\alpha \beta }u^\alpha u^\beta `$ and $`\rho _t=(T_{\alpha \beta }\frac{1}{2}Tg_{\alpha \beta })u^\alpha u^\beta `$ are the energy density measured by a static observer and the convergence density felt by a timelike congruence respectively ($`u^\alpha u_\alpha =1`$).

From Eq. (4) we have that $`T=0`$. This specific restriction on the form of the energy–momentum tensor automatically leads to a class of wormhole solutions. Since we are interested in Einstein wormholes, we conclude that the scalar curvature $`R=0`$. This constraint will be a condition on the shape function $`b(r)`$ and on the red–shift function $`\varphi (r)`$ and on their derivatives. For obtaining the n–dimensional self–dual wormhole solution, we first demand $`\rho =0`$ from which we obtain $`b(r)`$, and then solve $`T=R=0`$ which would determine the function $`\varphi (r)`$. It is interesting to note that the most general solution of Eq. (4) automatically incorporates the requirement of the existence of a throat without horizons, i.e. Constraint 1 enumerated above is satisfied.

## III n–dimensional self–dual Lorentzian wormholes

### III.1 General $`R=0`$ solution

For the spherically symmetric wormhole in higher dimensions we shall consider the spacetime given by

$`ds^2=e^{2\varphi (r)}dt^2+{\displaystyle \frac{dr^2}{1\frac{b(r)}{r}}}+r^2d\mathrm{\Omega }_{n2}^2,`$ (5)
where now

$`d\mathrm{\Omega }_{n2}^2=d\theta _2^2+sin^2\theta _2d\theta _3^2+\mathrm{}..+{\displaystyle \underset{i=3}{\overset{n2}{}}}sin^2\theta _id\theta _{n1}^2.`$ (6)
In other words we have replaced the two–sphere of metric (1) by a (n-2)–sphere. In our notation the angular coordinates are denoted by $`\theta _i`$, where $`i`$ runs from 2 to $`(n1)`$ and $`n`$ is the dimensionality of the space-time. Note that in this notation there is no angular coordinate $`\theta _1`$.

We now introduce the proper orthonormal basis as

$`ds^2=\theta ^{(0)}\theta ^{(0)}+\theta ^{(1)}\theta ^{(1)}+\theta ^{(2)}\theta ^{(2)}+`$
$`\theta ^{(3)}\theta ^{(3)}+{\displaystyle \underset{i=4}{\overset{n1}{}}}\theta ^{(i)}\theta ^{(i)},`$ (7)
where the basis one–forms $`\theta ^{(\alpha )}`$ (here the index $`\alpha `$ runs from $`0`$ to $`(n1)`$) are given by

$`\theta ^{(0)}=e^{\varphi (r)}dt,`$
$`\theta ^{(1)}={\displaystyle \frac{dr}{\sqrt{1\frac{b(r)}{r}}}},`$
$`\theta ^{(2)}=rd\theta _2,`$
$`\theta ^{(3)}=rsin\theta _2d\theta _3,\mathrm{}..,`$
$`\theta ^{(n1)}`$ $`=`$ $`r{\displaystyle \underset{i=2}{\overset{n2}{}}}sin\theta _id\theta _{n1}.`$
From these expressions we obtain for the non–null components of the Einstein tensor:

$`G_{(0)(0)}={\displaystyle \frac{(n2)}{2r^3}}\left[{\displaystyle \frac{}{}}(n4)b+rb^{}{\displaystyle \frac{}{}}\right],`$ (8)
$`G_{(1)(1)}={\displaystyle \frac{(n2)}{2r^3}}\left[{\displaystyle \frac{}{}}(n3)b+2r\varphi ^{}(br){\displaystyle \frac{}{}}\right],`$ (9)
$`G_{(2)(2)}={\displaystyle \frac{1}{2r^3}}[{\displaystyle \frac{}{}}2r^2(br)(\varphi ^{\prime \prime }+\varphi ^2)`$
$`+r(rb^{}7b2nr+2nb+6r)\varphi ^{}+b(158n)`$
$`+rb^{}(n3)+n^2b{\displaystyle \frac{}{}}],`$ (10)
and

$`G_{(3)(3)}=G_{(4)(4)}=\mathrm{}..=G_{(n1)(n1)}=G_{(2)(2)},`$ (11)
where the prime denotes a derivative with respect to r.

The curvature scalar is given by

$`R={\displaystyle \frac{n2}{2r^3}}[{\displaystyle \frac{}{}}2r^2(br)(\varphi ^{\prime \prime }+\varphi ^2)+({\displaystyle \frac{}{}}r^2b^{}+2r^2(2n)`$
$`+rb(2n5){\displaystyle \frac{}{}})\varphi ^{}+(n4)(n2)b+rb^{}(n2){\displaystyle \frac{}{}}].`$
We define the diagonal energy–momentum tensor components as

$`T_{(0)(0)}=\rho (r),T_{(1)(1)}=\tau (r),`$
$`T_{(2)(2)}=T_{(3)(3)}=\mathrm{}..=T_{(n1)(n1)}=p(r).`$ (13)
Here $`T_{(2)(2)}=T_{(3)(3)}=\mathrm{}..=T_{(n1)(n1)}`$, in view that we have a spherically symmetric space–time.

Using the Einstein equations

$`G_{(\alpha )(\beta )}=R_{(\alpha )(\beta )}{\displaystyle \frac{R}{2}}g_{(\alpha )(\beta )}=\kappa T_{(\alpha )(\beta )},`$ (14)
where $`\kappa =8\pi G`$, we find from (5) that

$`\kappa \rho (r)={\displaystyle \frac{(n2)}{2r^3}}\left[{\displaystyle \frac{}{}}(n4)b+rb^{}{\displaystyle \frac{}{}}\right],`$ (15)
$`\kappa \tau (r)={\displaystyle \frac{(n2)}{2r^3}}\left[{\displaystyle \frac{}{}}(n3)b+2r\varphi ^{}(br){\displaystyle \frac{}{}}\right],`$ (16)
$`\kappa p(r)={\displaystyle \frac{1}{2r^3}}[{\displaystyle \frac{}{}}2r^2(br)(\varphi ^{\prime \prime }+\varphi ^2)`$
$`+r(rb^{}7b2nr+2nb+6r)\varphi ^{}+b(158n)`$
$`+rb^{}(n3)+n^2b{\displaystyle \frac{}{}}].`$ (17)
Here $`\tau (r)`$ is the radial pressure $`p_r`$ (and differs by a minus sign from the conventions of Morris and Thorne Morris ) and $`p(r)`$ is the transverse pressure $`p_t`$.

Considering the condition of self–duality $`R=T=0`$ we find the following equation:

$`\varphi ^{\prime \prime }+\varphi ^2+\left({\displaystyle \frac{rb^{}+b(2n5)+2r(2n)}{2r(br)}}\right)\varphi ^{}`$
$`+{\displaystyle \frac{(n4)(n2)b+rb^{}(n2)}{2r^2(br)}}=0.`$ (18)
This equation can be thought of as the master equation for all n–dimensional static spherically symmetric $`R=0`$ geometries.

Given the function $`b(r)`$ one can solve equation (III.1) to obtain $`\varphi (r)`$. We shall find the function $`b(r)`$ from the self–dual condition. This implies that $`\rho (r)=0`$ and then, from Eq. (15), we have

$`b(r)=2mr^{4n}.`$ (19)
Here we have written the constant of integration as $`2m`$ in order to obtain the mass $`m`$ in the four dimensional Schwarzschild case. Then Eq. (III.1) simplifies to

$`\varphi ^{\prime \prime }+\varphi ^2+\left({\displaystyle \frac{nmr^3mr^3+2r^nnr^n}{2mr^4r^{n+1}}}\right)\varphi ^{}=0.`$ (20)
The solution of this nonlinear differential equation may be written as

$`\varphi (r)=ln\left(k+\lambda \sqrt{1{\displaystyle \frac{2m}{r^{n3}}}}\right),`$ (21)
where $`k`$ and $`\lambda `$ are constants of integration. This implies that the line element (5) takes the form

$`ds^2=\left(k+\lambda \sqrt{1{\displaystyle \frac{2m}{r^{n3}}}}\right)^2dt^2`$
$`+{\displaystyle \frac{dr^2}{1\frac{2m}{r^{n3}}}}+r^2d\mathrm{\Omega }_{n2}^2.`$ (22)
The components of the energy–momentum tensor are given by

$`\rho (r)=0,`$ (23)
$`\kappa \tau (r)={\displaystyle \frac{k(n3)(n2)mr^{1n}}{k+\lambda \sqrt{1\frac{2m}{r^{n3}}}}},`$ (24)
and

$`\kappa p(r)={\displaystyle \frac{k(n3)mr^{1n}}{k+\lambda \sqrt{1\frac{2m}{r^{n3}}}}}.`$ (25)
These expressions satisfy the constraint for the trace of the energy–momentum tensor:

$`T=T_{(\alpha )(\beta )}g^{(\alpha )(\beta )}=\rho (r)+\tau (r)+(n2)p(r)=0.`$
Note that from equations (III.1)–(25), for $`n=4`$ we obtain the 4–dimensional expressions (9), (10), (11) and (12) of Ref. Dadhich .

For $`n=3`$ the Eq. (21) does not represent the general solution for the differential equation (20), since the solution (21) depends on only one integration constant. The general solution now will be given by

$`ds^2=(k+\lambda \mathrm{ln}r)^2dt^2+{\displaystyle \frac{dr^2}{12m}}+r^2d\theta ^2,`$ (26)
where $`k`$ and $`\lambda `$ are the constants of integration and

$`\rho =0,`$
$`\kappa \tau (r)=\kappa p(r)={\displaystyle \frac{\lambda (12m)}{(k+\lambda \mathrm{ln}r)r^2}},`$
are the components of the energy–momentum tensor. The resulting spacetime is singular at $`r_1=0`$ and $`r_2=e^{k/\lambda }`$. If $`k>>0`$ or $`\lambda 0`$, then the singular radius $`r_20`$.

If we set $`\lambda =0`$, we have from (26) a vacuum solution which is locally flat, but conical in form. This metric is analogous to the Schwarzschild metric around a point mass in four dimensions. However, this metric does not lead to a black hole Star , and then also there is no three–dimensional Schwarzschild wormhole.

For $`n=2`$ the metric (III.1) is not the general self–dual solution, since in (1+1)–gravity the Einstein tensor vanishes identically, so that the self–dual condition (4) is identically satisfied.

Thus, in the following subsection we shall consider that $`n4`$.

### III.2 Black holes, naked singularities and wormholes

Within the framework of the obtained family of solutions there are three classes of spherically symmetric spacetimes: black hole, nakedly singular and wormhole geometries. For example, the n–dimensional vacuum Schwarzschild geometry Myers  is obtained when $`k=0`$. If $`m<0`$, we have a naked singularity (for any value of $`k`$ and of $`\lambda `$). The n–dimensional spatial–Schwarzschild traversable wormhole is obtained when $`\lambda =0`$.

We are interested in the interpretation of the obtained solution as a Lorentzian wormhole. The weak energy condition ($`\rho 0`$, $`\rho +\tau 0`$, $`\rho +p0`$) and null energy condition ($`\rho +\tau 0`$, $`\rho +p0`$) are both violated by Eqs. (23)–(25). Effectively, we have here that $`\rho =0`$; then we obtain $`\tau 0`$ and $`p0`$. But $`T=0`$ implies that $`\tau =2p`$, thus, if $`p0`$, we have $`\tau 0`$ (and vice-versa). The extent of the energy condition violation, caused by the behavior of $`r^{1n}`$, for $`n4`$, is large in the vicinity of the throat. One does have a control parameter $`k`$ which can be chosen to be very small in order to restrict the amount of violation.

In the following, we shall follow the procedure of Dadhich et al. Dadhich . To really make the wormhole explicit we need two coordinate patches:

$`ds^2=\left(k+\lambda \sqrt{1{\displaystyle \frac{2m}{r_1^{n3}}}}\right)^2dt^2`$
$`+{\displaystyle \frac{dr_1^2}{1\frac{2m}{r_1^{n3}}}}+r_1^2d\mathrm{\Omega }_{n2}^2,`$ (27)
where $`(2m)^{1/(n3)}r_1\mathrm{}`$ and

$`ds^2=\left(k\lambda \sqrt{1{\displaystyle \frac{2m}{r_2^{n3}}}}\right)^2dt^2`$
$`+{\displaystyle \frac{dr_2^2}{1\frac{2m}{r_2^{n3}}}}+r_2^2d\mathrm{\Omega }_{n2}^2,`$ (28)
where $`(2m)^{1/(n3)}r_2\mathrm{}`$.

We have to sew these patches together at $`r=r_1=r_2=(2m)^{1/(n3)}`$. To make this clearer, it is convenient to go to isotropic coordinates. The advantage of these coordinates is that in almost all cases a single coordinate patch covers the entire space–time.

In isotropic coordinates, the metric in a slice $`t=`$ constant is conformal to the metric of Euclidean (n-1)–space. We consider a transformation in which the angular coordinates $`\theta _2`$$`\theta _{n1}`$ and $`t`$ remain unchanged while the radial coordinate

$`r\overline{r}=\overline{r}(r),`$ (29)
so that $`\overline{r}`$ is some other radial coordinate, where the metric (III.1) takes the form

$`ds^2=\left(k+\lambda \sqrt{1{\displaystyle \frac{2m}{r^{n3}}}}\right)^2dt^2`$
$`+\lambda ^2(\overline{r})[d\overline{r}^2+\overline{r}^2d\mathrm{\Omega }_{n2}^2].`$ (30)
Comparing this metric with (III.1) we obtain $`r^2=\lambda ^2(\overline{r})\overline{r}^2`$ and the following ordinary differential equation:

$`{\displaystyle \frac{dr}{\sqrt{r^22mr^{5n}}}}=\pm {\displaystyle \frac{d\overline{r}}{\overline{r}}}.`$ (31)
Since we require $`\overline{r}\mathrm{}`$ as $`r\mathrm{}`$, we take the plus sign. Integrating the latter expression we find

$`r=\overline{r}\left[2^{n4}\left(1+{\displaystyle \frac{m}{(2\overline{r})^{n3}}}\right)^2\right]^{1/(n3)}.`$ (32)
Note that, when $`\overline{r}0`$ or $`\overline{r}\mathrm{}`$, the coordinate $`r\mathrm{}`$ for $`n4`$.

When $`n=4`$, we obtain exactly the same transformation for going from curvature coordinates to isotropic coordinates as was used for Schwarzschild itself. In this case of course the transformation (32) carries the n–dimensional Schwarzschild metric into isotropic form, since the space part of the metric (III.1) is identical to the space part of the higher dimensional Schwarzschild version.

Thus by (III.1) and (32) the line element, in terms of isotropic coordinates, is given by

$`ds^2=\left(k+\lambda \left[{\displaystyle \frac{\frac{m}{(2\overline{r})^{n3}}1}{\frac{m}{(2\overline{r})^{n3}}+1}}\right]\right)^2dt^2`$
$`+\left[2^{n4}\left(1+{\displaystyle \frac{m}{(2\overline{r})^{n3}}}\right)^2\right]^{2/(n3)}[d\overline{r}^2+\overline{r}^2d\mathrm{\Omega }_{n2}^2].`$ (33)
Note that from this equation for $`n=4`$, we obtain the 4–dimensional expression (15) of Ref. Dadhich .

It can be shown that both metrics (III.2) and (III.2) take the isotropic form (III.2) with the help of transformation (32). Then we have a single global coordinate chart for the alleged traversable Lorentzian wormhole. In this case $`r0`$ is one of the asymptotically flat regions and $`r\mathrm{}`$ is the other one.

In order to have a traversable wormhole, we need to know the ranges of the parameters $`k`$ and $`\lambda `$ for which we have no horizon, i.e. the $`g_{tt}`$ component does not go to zero. We suppose $`m>0`$, in order to have no naked singularities. There is a possible horizon when $`g_{tt}=0`$, thus

$`k\left({\displaystyle \frac{m}{(2\overline{r})^{n3}}}+1\right)+\lambda \left({\displaystyle \frac{m}{(2\overline{r})^{n3}}}1\right)=0.`$ (34)
Solving this equation we obtain

$`\overline{r}__H={\displaystyle \frac{1}{2}}\left[{\displaystyle \frac{m(\lambda k)}{\lambda +k}}\right]^{1/(n3)}.`$ (35)
In order to have a horizon, the radius $`\overline{r}__H`$ must be positive; then we have

$`{\displaystyle \frac{\lambda k}{\lambda +k}}0.`$ (36)
One can show that this horizon is actually a naked curvature singularity.

To see this more clearly, we calculate the radial and transverse pressure:

$`\kappa \tau =\kappa (n2)p=`$
$`{\displaystyle \frac{k(n3)(n2)m\left[(2\overline{r})^{n3}+m\right]^{2(1n)/(n3)}}{2^{(1n)/(n3)}(2\overline{r})^{1n}\sqrt{g_{tt}}}},`$ (37)
and we conclude that both pressures diverge as $`g_{tt}0`$. Thus, if the parameters $`\lambda `$ and $`k`$ satisfy the inequalities

$`\lambda +k>0and\lambda k>0,`$ (38)
or

$`\lambda +k<0and\lambda k<0;`$ (39)
we have naked singularities. If the parameters $`\lambda `$ and $`k`$ do not satisfy Eqs. (38) nor (39), then Constraint 1 enumerated above is satisfied, and curvature singularities do not form, the $`g_{tt}`$ components of the metric never go to zero, and we have a traversable wormhole.

We enumerate now some other properties of the obtained geometry:

(1) The geometry is invariant under simultaneous sign flips $`\lambda \lambda `$ and $`kk`$, independently of the dimensions of the space–time.

(2) $`k=0`$, $`\lambda 0`$ is the n–dimensional Schwarzschild geometry; it is a non–traversable wormhole (in this case the isotropic coordinate does not cover the entire manifold).

(3) $`\lambda =0`$, $`k0`$ is the zero–tidal–force spatial–Schwarzschild traversable wormhole (the manifold is covered completely by the isotropic coordinate system)

(4) $`\lambda =0`$, $`k=0`$ is singular, independently of the dimensions of the space–time.

(5) At the throat $`g_{tt}(r=[2m]^{1/(n3)})=k^2`$, so $`k0`$ is required to ensure traversability.

(6) $`g_{tt}(\overline{r}=\mathrm{})=(k\lambda )^2`$ and $`g_{tt}(\overline{r}=0)=(k+\lambda )^2`$; then we see that time runs at different rates in the two asymptotic regions.

## IV Concluding remarks

Our aim in this paper has been to obtain self–dual Lorentzian wormholes in the framework of n–dimensional Einstein gravity. For this we have followed the prescription provided by Dadhich et al. Dadhich  for obtaining wormholes. They have proposed one such prescription which is characterized by the equation $`\rho =\rho _t=0`$, which implies that $`R=0`$ and, equivalently, a traceless energy–momentum tensor. This constraint gives a condition on the shape function $`b(r)`$ and on the red–shift function $`\varphi (r)`$ and on their derivatives.

For obtaining the n–dimensional self–dual wormhole solution, we first demand $`\rho =0`$ from which we obtain $`b(r)`$, and then solve $`T=R=0`$ which would determine the function $`\varphi (r)`$.

The resulting geometry represents a family of spacetimes which contains Lorentzian wormholes, naked singularities, and the n–dimensional Schwarzschild black hole. However, in lower dimensional Einstein gravity, without cosmological constant, we can not have self–dual Lorentzian wormholes.

The isotropic coordinates are used to display the full structure of the obtained higher dimensional geometry.

In this case, of course the wormhole geometry has exotic matter as the source, i.e. the energy–momentum tensor of the matter explicitly violates the energy conditions. This fact can not be used to rule out wormhole solutions. Today many physical situations are known in which the energy conditions are violated Dadhich ; Visser1 .

## V Acknowledgements

The authors thank Carol Muñoz for typing this manuscript and S. del Campo, N. Cruz and S. Lepe for valuable comments. This work was supported by CONICYT through Grant FONDECYT N<sup>0</sup> 1010485 and by Dirección de Promoción y Desarrollo de la Universidad del Bío–Bío.