Poisson-Boltzmann equation

A mean-field coupling of the Poisson equation to an ideal Boltzmann distribution of mobile ions. In Gaussian units with uniform dielectric constant $ϵ$, ${\nabla }^2\varphi =-(4\pi /ϵ)[{\rho }_f+{\sum }_i{q}_i{n}_{i,0}{e}^{-\beta q_i\varphi }]$. The potential reference and chemical potentials determine the normalization factors. It neglects discrete-ion correlations and assumes local thermal equilibrium. A counterion-only model is not the same equation as a symmetric salt reservoir.

Confine the counterions of a uniformly charged infinite cylinder within a coaxial cylinder of radius $R$, with total mobile line charge $\lambda$. The electric field vanishes at $R$, while its surface value at $a$ is fixed by the bare line charge. This gives $a{\varphi }^{\prime }(a)=2\lambda /ϵ$ and $R{\varphi }^{\prime }(R)=0$ in Gaussian units. Sending $R/a\to \infty$ defines the infinite-dilution limit of cylindrical counterions.

In a neutral counterion-only cylindrical cell, send the outer radius to infinity at fixed cylinder charge. Below the Manning parameter threshold, number density tends to zero at each fixed radius. Above threshold, the cylindrical counterion-only Poisson-Boltzmann profile retains line charge $\lambda -q/{\ell }_B$ locally, while the rest recedes to infinity. Therefore the limit of the full finite-cell charge integral is not the charge integral of the pointwise limiting density.

For $u=\log (r/a)$ and $\Phi =\beta q\varphi -2u$, a counterion-only Poisson-Boltzmann equation reduces to ${\Phi }^{\prime \prime }=-C{e}^{-\Phi }$. Conditions $\Phi (0)=0$, $\Phi \to \infty$ and ${\Phi }^{\prime }\to 0$ give $\Phi =2\log (1+bu)$, $b=\sqrt{C/2}>0$. Matching surface Gauss's law gives $b=\eta -1$, so this branch requires the Manning parameter $\eta >1$. Its number density is $n(r)=(\eta -1{)}^2(a/r{)}^2/[2\pi {\ell }_B{a}^2(1+(\eta -1)\log (r/a){)}^2]$. It leaves residual line-charge magnitude $q/{\ell }_B$.

Localization of a finite fraction of oppositely charged ions near a charged object even as the confining volume grows without bound. In the salt-free infinite-cylinder mean-field model, the Manning parameter must exceed one for a nonzero limiting local density. The condensed charge does not include ions that escape to infinity; finite-cell charge neutrality and the local infinite-volume limit must not be interchanged.

In the mean-field infinite-dilution cylinder model, the fraction of neutralizing charge that remains localized is $f_c=\max (1-1/\eta ,0)$, where $\eta$ is the Manning parameter. For $\eta >1$, integrating the cylindrical counterion-only Poisson-Boltzmann profile gives $Q_c=\lambda -q/{\ell }_B$. Below threshold, the local limiting density vanishes even though every finite neutral cell contains the full counterion charge.

The positive mobile charge per unit axial length accumulated from cylinder radius $a$ to $r$ is $Q(r)=2\pi {\int }_a^{r}s\rho (s)ds$. For fixed negative line charge $-\lambda$, Gauss's law gives signed radial electric field $E_r=2[-\lambda +Q(r)]/(ϵr)$ in Gaussian units. Its absolute value is the field magnitude. An integral over a local infinite-dilution profile measures condensed charge, rather than every ion in a finite neutral cell.

The dimensionless line-charge coupling $\eta =\lambda {\ell }_B/q$, with negative cylinder line charge $-\lambda$ and counterions of charge $q>0$. Here the Bjerrum length uses the same reference charge $q$. The mean-field infinite-dilution threshold is $\eta =1$. If ${\ell }_B$ is instead tabulated for elementary charge $e$ and counterions have charge $ze$, the corresponding coupling is $z\lambda {\ell }_B/e$.