# Dynamics of Counterion Condensation

## Abstract

Using a generalization of the Poisson-Boltzmann equation, dynamics of counterion condensation is studied. For a single charged plate in the presence of counterions, it is shown that the approach to equilibrium is diffusive. In the far from equilibrium case of a moving charged plate, a dynamical counterion condensation transition occurs at a critical velocity. The complex dynamic behavior of the counterion cloud is shown to lead to a novel nonlinear force–velocity relation for the moving plate.

Many experimental techniques used to probe properties of macroions involve setting them to motion by applying some external driving mechanism (such as migration in an applied electric field or hydrodynamic flow, sedimentation, etc.), and monitoring the dynamical response. A macroion in solution is surrounded by an accompanying cloud of counterions, and the corresponding response of the counterions is in general very complex. This often makes interpretation of the observed properties of the dynamically perturbed system a nontrivial task.

For example, it is known that if a macroion moves, the asymmetry set by the motion causes a distortion in the counterion cloud. The distorted cloud, in turn, produces a nonzero electric field (called the asymmetry field ) that opposes the motion of the macroion. This phenomenon is known as the “relaxation effect,” and has been studied in the literature within the Debye-Hückel (DH) theory. The approximate DH description, which is based on a linearization of the nonlinear Poisson-Boltzmann (PB) equation, is however known to break down when the macroions are highly charged. In particular, it does not capture the phenomenon of counterion condensation, about which a lot has been learned by examining the available exact solutions of the full nonlinear equilibrium PB equation .

In this Letter, we develop a dynamical generalization of the nonlinear PB equation, which we use to study the dynamical aspects of counterion condensation. For the specific example of a single charged plate in the presence of counterions, we show that the equilibrium, corresponding to a Gouy-Chapman profile, is approached diffusively. In the far from equilibrium case of a moving charged plate we present an exact stationary solution of the dynamical PB equation, and show that the cloud of counterions phase separates into a comoving part and a condensate of the excess charge which is expelled to infinity. The amount of the comoving charge depends on the velocity of the plate, and is decreased as the velocity increases. At some critical velocity $`v_c`$, the system undergoes a dynamical phase transition, and eventually all the counterions evaporate from the neighborhood of the moving plate. We show that this leads to a novel nonlinear force–velocity relation for the moving charged plate in the presence of the counterions.

To study the dynamics of counterions in the presence of macroions, one needs to formulate a dynamical generalization of the PB equation. Consider a set of negatively charged macroions described by the given charge density $`\rho _m(𝐱,t)`$, embedded in a cloud of positively charged counterions with concentration $`c(𝐱,t)`$. The electric potential $`\varphi `$(x,t) is then given by the solution of the Poisson equation:

$$^2\varphi =\frac{4\pi }{ϵ}(ec+\rho _m),$$
(1)   
in which $`ϵ`$ is the dielectric constant of the solvent, and $`e`$ is the electron charge. The dynamics of $`c(𝐱,t)`$ is governed by a continuity equation of the form $`_tc+𝐉=0`$, in which the current density $`𝐉`$ is composed of a deterministic part $`c𝐯`$, and a stochastic part $`Dc`$ as given by Fick’s law, where $`𝐯(𝐱,t)`$ is the velocity field, and $`D`$ is the diffusion constant of the counterions. In a mean-field approximation, the velocity field at each point is determined by the local value of the electric field $`𝐄(𝐱,t)`$ as $`𝐯=\mu 𝐄=\mu \varphi `$, where $`\mu `$ is the electric mobility of the counterions. Using the self-consistency relation in the continuity equation, one obtains the so-called Nernst-Planck equation

$$_tc=D^2c+\mu (c\varphi ).$$
(2)   
Note that we have simplified the problem by neglecting any couplings to the hydrodynamics of the solvent. The above two equations (Eqs.(1) and (2)) describe the nonlinear dynamics of counterions in the presence of a given distribution of macroions. At equilibrium, $`_tc=0`$ and Eq.(2) yields $`c\mathrm{exp}(\mu \varphi /D)`$, where equilibration at a temperature $`T`$ implies an Einstein relation $`D=(\mu /e)k_BT`$. Inserting the Boltzmann form for $`c`$ back into Eq.(1) then yields the PB equation. In analogy to the equilibrium case, we can define a dynamical Bjerrum length $`\mathrm{}_B=e\mu /ϵD`$.

The above nonlinear equations are in general very difficult to solve, which is why they are usually dealt with in a linearized approximation . However, the approximation is known to break down in the neighborhood of highly charged surfaces, where interesting phenomena such as counterion condensation take place. To capture the essence of the nonlinearity in the dynamical context, we restrict ourselves to a one dimensional case where the equations prove to be more tractable. Eliminating the concentration field $`c`$ from the two equations, one obtains an equation for the electrostatic potential, which can be integrated twice to yield

$`_t\varphi (x,t)_t\varphi (\mathrm{},t)=D_x^2\varphi +{\displaystyle \frac{\mu }{2}}(_x\varphi )^2+{\displaystyle \frac{4\pi }{ϵ}}{\displaystyle _{\mathrm{}}^x}𝑑x^{}\left[\mu \rho _m(x^{},t)_x\varphi (x^{},t)+D_x\rho _m(x^{},t)+J_m(x^{},t)\right],`$ (3)   
where the macroion current density $`J_m`$ is obtained from the continuity equation for the macroions $`_t\rho _m+_xJ_m=0`$, and the boundary condition $`E(\mathrm{},t)=0`$ has been implemented.

The above equation, which can be called a dynamical PB equation , belongs to the general class of the celebrated Kardar-Parisi-Zhang (KPZ) equations , with the coupling to the source appearing both in the additive and multiplicative forms. It is however important to note that in this context the sources represent slower dynamical degrees of freedom corresponding to the motion of the macroions (compared to counterions), which makes it somewhat different from the standard KPZ problems .

To study how counterions dynamically rearrange themselves around macroions, we focus on the specific example of a single negatively charged plate with charge (number) density $`\sigma `$ and surface area $`A`$, which is moving at a constant velocity $`v`$, i.e., $`\rho _m(x,t)=e\sigma \delta (xvt)`$. Using a Cole-Hopf transformation $`\varphi (x,t)\varphi (\mathrm{},t)=2D/\mu \mathrm{ln}W(x,t)`$ , Eq.(3) can be written as

$`_tW`$ $`=`$ $`D_x^2W`$ (4)   
$``$ $`{\displaystyle \frac{2D}{\lambda }}\left[\delta (xvt)+\left({\displaystyle \frac{v\mu E_0}{D}}\right)\mathrm{\Theta }(xvt)\right]W,`$ (5)   
where $`E_0(t)=2D/\mu _x\mathrm{ln}W|_{x=vt}`$ is the asymmetry field, $`\mathrm{\Theta }(x)`$ is the step function, and $`\lambda =1/\pi \sigma \mathrm{}_B`$ is a dynamical Gouy-Chapman length. Note that despite its simple form, this diffusion-like equation is still nonlinear due to the self-consistent coupling of the asymmetry field (electric field at the charged plate).

Let us first assume that the plate is not moving ($`v=0`$), and ask how the equilibrium configuration is dynamically approached. If we assume that the initial configuration of the counterions is symmetric with respect to the plate, the symmetry will be conserved during time evolution rendering $`E_0(t)=0`$ at all times. This simplifies Eq.(4) to a linear diffusion equation which can be solved exactly. One obtains

$$\frac{e\varphi (x,t)}{k_BT}=2\mathrm{ln}\left\{1+\frac{|x|}{\lambda }+_{\mathrm{}}^+\mathrm{}𝑑x^{}\left[\mathrm{exp}\left(\frac{e\varphi (x^{},0)}{2k_BT}\right)1\frac{|x^{}|}{\lambda }\right]\times \frac{1}{\sqrt{4\pi Dt}}\mathrm{exp}\left[\frac{(xx^{})^2}{4Dt}\right]\right\}.$$
(6)   
In simple terms this means that the equilibrium Gouy-Chapman profile diffusively develops, as the initial configuration diffusively disappears. Naively, one might not expect such an amazingly simple behavior from a fully interacting Coulomb system.

For a stationary plate at equilibrium, all the counterions are known to be “condensed” in a Gouy-Chapman (density) profile which decays algebraically at large separations (see below). It is interesting to study this problem in the far from equilibrium case of a moving plate. In particular, we may ask if there is a stationary solution of Eq.(4), of the form $`W(x,t)=W(xvt)`$, in which all the counterions are comoving with the plate at the velocity $`v`$. The answer to this question turns out to be negative. Apparently, the Coulomb attraction which could overcome the combination of entropy and repulsion among the counterions in the equilibrium case, is not capable of accommodating the viscous drag of all the counterions in this balance, for any nonzero $`v`$. However, we can find stationary solutions if we do not require that all the counterions are comoving.

Such solutions can be shown to exist only for negative values of $`v`$, with a boundary condition that requires a specific value for the electric field at $`+\mathrm{}`$. This implies that the neutralizing counterion cloud actually phase separates into a comoving domain and a domain of excess charges accumulated at $`+\mathrm{}`$, as required by this one dimensional model . This class of solutions is parametrized by the number of comoving counterions. The stationary solution of Eq.(4) with maximum number of comoving counterions can be obtained as 

$$W(x,t)=\{\begin{array}{cc}1\left(\frac{1+\lambda v/4D}{1\lambda v/4D}\right)^2\mathrm{exp}\left[\frac{v(xvt)}{D}\right],\hfill & \mathrm{for}x<vt,\hfill \\ & \\ \frac{\left(\lambda v/D\right)}{(1\lambda v/4D)^2}\left\{1+\left[1\left(\frac{\lambda v}{4D}\right)^2\right]\frac{(xvt)}{\lambda }\right\}\mathrm{exp}\left[\frac{v(xvt)}{2D}\right],\hfill & \mathrm{for}x>vt,\hfill \end{array}$$
(7)   
and correspondingly for the counterion density profile as

$$c(x,t)=\{\begin{array}{cc}\frac{(v/D)^2}{2\pi \mathrm{}_B}\frac{\left(\frac{1+\lambda v/4D}{1\lambda v/4D}\right)^2\mathrm{exp}\left[\frac{v(xvt)}{D}\right]}{\left\{1\left(\frac{1+\lambda v/4D}{1\lambda v/4D}\right)^2\mathrm{exp}\left[\frac{v(xvt)}{D}\right]\right\}^2},\hfill & \mathrm{for}x<vt,\hfill \\ & \\ \frac{1}{2\pi \mathrm{}_B\lambda ^2}\frac{\left[1\left(\lambda v/4D\right)^2\right]^2}{\left\{1+\left[1\left(\lambda v/4D\right)^2\right]\left(\frac{xvt}{\lambda }\right)\right\}^2},\hfill & \mathrm{for}x>vt.\hfill \end{array}$$
(8)   
The above solution has very interesting features. In the limit $`v0`$, Eq.(8) reduces to the equilibrium Gouy-Chapman profile 

$$c_{\mathrm{eq}}(x)=\frac{1}{2\pi \mathrm{}_B\lambda ^2}\times \frac{1}{\left(1+\frac{|x|}{\lambda }\right)^2}.$$
(9)   
In this limit, all the counterions are condensed, typically at a distance given by $`\lambda `$, although the profile has an algebraic decay.

For a nonzero $`v`$, while the density profile is still algebraically decaying “behind” the moving plate (for $`x>vt`$), it decays exponentially “ahead” of the moving plate (for $`x<vt`$), indicating a jamming of the profile as a result of the motion. In the comoving profile of counterions, there is a total charge of $`Q_>=\frac{1}{2}Q_0[1(\lambda v/4D)^2]`$ behind the plate, as opposed to $`Q_<=\frac{1}{2}Q_0[1+(\lambda v/4D)^2+\lambda v/2D]`$ ahead of the plate, where $`Q_0=e\sigma A`$ is the overall charge of the counterions. Note that the comoving counterions are distributed asymmetrically with $`Q_>>Q_<`$. The amount of the excess charge can be easily obtained as

$$Q_{\mathrm{ex}}(v)=Q_0Q_>Q_<=\frac{eA}{4\pi \mathrm{}_B}\times \frac{|v|}{D},$$
(10)   
which is independent of $`\sigma `$. By examining the asymptotic limit of the electric field at infinity, one can easily see that this excess charge is indeed expelled to $`+\mathrm{}`$.

As the velocity of the plate increases, the number of comoving counterions decreases, until at $`\lambda v/4D=1`$ eventually all the counterions evaporate to infinity. This corresponds to a dynamical counterion condensation phase transition, happening at the critical velocity $`v_c=4D/\lambda `$, and is similar to the equilibrium transition in the case of a charged cylinder . It is easy to check from Eq.(8) that the density profile of the comoving counterions vanishes on both sides at $`\lambda v/4D=1`$.

The solution of Eq.(7) yields a value $`E_0=(1+\lambda v/8D)v/\mu `$ for the asymmetry field at the position of the plate, which leads to a very interesting mechanical response for the charged plate . In the stationary situation, the total force $`F_{\mathrm{tot}}`$ exerted on the charged plate should vanish. This means that an externally applied (mechanical) force $`F_{\mathrm{ext}}`$ (that is necessary to maintain the constant velocity motion) should balance an electrical contribution due to nonzero value of the electric field $`E_0`$ felt by the charged plate, namely, $`F_{\mathrm{ext}}Q_0E_0=0`$. Inserting the velocity dependent value for $`E_0`$, one obtains

$$|F_{\mathrm{ext}}|=\{\begin{array}{cc}\left(Q_0/\mu \right)|v|\frac{ϵ}{8\pi }\left(v/\mu \right)^2A,\hfill & \mathrm{for}|v|<v_c,\hfill \\ & \\ 2\pi Q_0^2/ϵA,\hfill & \mathrm{for}|v|v_c,\hfill \end{array}$$
(11)   
as the force–velocity relation for a moving charged plate. A plot of Eq.(11) is sketched in Fig. 1, in which $`F_c=2\pi Q_0^2/ϵA`$.

In the limit of very low velocities ($`|v|v_c`$), one can neglect the quadratic velocity term in Eq.(11). This leads to a viscous drag with an effective friction coefficient $`\zeta _{\mathrm{eff}}=Q_0/\mu `$, where the “electrostatic friction” is due to dissipation corresponding to the comoving could of counterions. Note that all the counterions are condensed in this limit, and participate in the dissipation. In the opposite limit of $`|v|v_c`$, no counterions are condensed and the friction coefficient is consequently zero. However, since all the counterions participate in forming a condensate at infinity, there is a constant (independent of velocity) electrostatic attractive force acting on the plate, which is simply the force between two parallel and equally charged plates. In fact, one can rewrite Eq.(11) in such a way that these features are manifest at any velocity: $`|F_{\mathrm{ext}}|=(Q_c(v)/\mu )|v|+2\pi Q_{\mathrm{ex}}(v)^2/ϵA`$, where $`Q_c(v)=Q_>+Q_<=Q_0Q_{\mathrm{ex}}(v)`$ is the amount of condensed (comoving) charge. Interestingly, the nonlinear response function

$$\zeta (v)\frac{F_{\mathrm{ext}}(v)}{v}=Q_c(v)/\mu ,$$
(12)   
gives a proper account of the number of condensed (comoving) counterions at any velocity.

The dynamical counterion condensation phase transition discussed above can be characterized by an order parameter, which is given by the number of condensed counterions. The tunning parameter for this dynamical transition is the external force, which is the analogue of temperature in the equilibrium case. In analogy to equilibrium critical phenomena, one can look at the critical exponents corresponding to the transition. For example, the order parameter vanishes at $`F_c`$ as $`Q_c(F_c|F_{\mathrm{ext}}|)^\beta `$, with a mean-field exponent $`\beta =1/2`$.

It is well known that at equilibrium counterion condensation is determined by dimensional considerations . In $`d`$ dimensions, a $`D`$ dimensional macroion of size $`L_{}`$ attracts a counterion at a perpendicular distance $`L_{}`$, with a Coulomb energy that goes like $`E_c1/L_{}^{dD2}`$. On the other hand, entropy of a particle confined in such a box can be obtained as $`S\mathrm{ln}(L_{}^DL_{}^{dD})`$. Comparing energy and entropy one obtains that for $`d<D+2`$ counterions tend to condense to minimize energy (lower values for $`L_{}`$ are favored), while for $`d>D+2`$ they prefer to be free and gain entropy (higher values for $`L_{}`$ are favored). The case $`d=D+2`$ is marginal, where a counterion condensation transition takes place . The analysis presented in this Letter clearly shows that this simple equilibrium picture is modified when the system is far from equilibrium. In particular, we found that complete condensation in the case of a charged plate will no longer hold for a moving plate. Another important difference is that, unlike the equilibrium case, there is a marked contrast between the condensed and the free counterions.

One might question the validity of the present formulation at high velocities such that $`\lambda v/D1`$, because of the assumption that the dynamics of the macroions is much slower compared to the counterions. The dimensionless parameter $`\lambda v/D`$ (often called the Péclet number) can be written as $`\tau _c/\tau _m`$, in which $`\tau _c`$ is the time it takes a counterion to diffuse a distance $`\lambda `$, whereas $`\tau _m`$ is the time in which the macroion drifts a same distance. It is thus possible that this ratio becomes comparable to 1, while the ratio between the corresponding diffusion times is still much less than unity.

In the derivation of Eq.(2), we have made use of a mean-field approximation similar to what is used to obtain the PB equation. It is well known that PB equation is incapable of describing intriguing phenomena such as attraction between like charged objects in the presence of condensed counterions, because of this approximation . One should then attempt to go beyond mean-field theory and study the effect of fluctuations on the dynamical PB equation along the lines of what has been done in the equilibrium case . In particular, it is shown in Ref.  that fluctuations lead to a stronger condensation, because mean-field theory overestimates the repulsion between counterions. It will thus be interesting to see how this effect competes with the viscous drag in the case of a moving plate. Another important and very interesting extension of this work would be to incorporate the coupling to hydrodynamics of the solvent, which we anticipate to have dramatic effects.

I am grateful to R. Bruinsma, M. Kardar, P. Pincus, M. Sahimi, and R. da Silveira for invaluable discussions and comments. This research was supported in part by the National Science Foundation under Grants No. PHY94-07194 and DMR-93-03667.