Electrostatics

Electrostatics studies time-independent electric fields and charge distributions.

Across a charged dielectric interface the tangential electric field is continuous and the normal displacement jump is the fixed surface charge density. Without a dipole sheet the electrostatic potential is continuous. For a charge sheet with equal permittivity on both sides, its normal potential derivative has jump $-{\sigma }_{\mathrm{fixed}}/\epsilon$. Setting the field to zero on one side is an additional physical boundary assumption, as in a conductor or a negligible-exterior-admittance idealization.

The Debye–Hückel approximation linearizes mobile-ion Boltzmann densities about a neutral bulk electrolyte. It is valid for ionic potential energies small compared with $k_{B}T$. The inverse Debye–Hückel screening length satisfies ${\kappa }_D^2={\sum }_i{n}_i{z}_i^2{e}^2/(\epsilon k_{B}T)$. The quadratic screened charging free energy includes both electric field energy and the linearized ionic-response term $\epsilon {\kappa }_D^2{\varphi }^2/2$.

A lateral sinusoidal surface charge density with wave number $k$ in the Debye–Hückel approximation generates vertical exponential or hyperbolic functions with inverse length $p=\sqrt{k^2+{\kappa }_D^2}$. In a homogeneous electrolyte filling all space, an isolated sheet at $z_s$ produces $\varphi ={\sigma }_k(x)e^{-p|z-z_s|}/(2\epsilon p)$. Boundary conditions determine the normalization when the electrolyte occupies only a gap.

Two equally modulated charge sheets in identical full-space electrolyte have charging energy per area ${\alpha }^2[1+e^{-pd}\cos \theta ]/(4\epsilon p)$, where $p=\sqrt{k^2+{\kappa }_D^2}$. Its phase-dependent interaction favors a half-wavelength offset, with opposite charge patches facing each other. For an electrolyte gap with negligible exterior displacement response, the energy is instead ${\alpha }^2[\coth (pd)+\cos \theta /\sinh (pd)]/(2\epsilon p)$, with the same minimizing phase. Absolute energies require specified exterior electrostatic interface boundary conditions.

For a chosen reference charge $q$, the separation at which its Coulomb interaction energy equals $k_{B}T$. The charge-$q$ convention is ${\ell }_B=q^2/(4\pi {ϵ}_{\mathrm{abs}}{k}_{B}T)$ in SI, or ${\ell }_B=\beta q^2/ϵ$ in Gaussian units. The commonly tabulated value uses the elementary charge; changing counterion valence requires tracking that reference convention. It sets the strength of counterion condensation.

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 $z\lambda {\ell }_B/e$.

Point charges $q_1,q_2$ separated by a displacement $r$ exert the force

The electric field vanishes inside a conductor at electrostatic equilibrium, so each connected conductor is equipotential and the exterior field is normal to its surface.

A Gaussian pillbox givesSince $E_{\mathrm{in}}=0$, the surface charge density is $\sigma ={ϵ}_0{E}_{\mathrm{out}}\cdot n$.

Surface charge density is electric charge per unit area. At a conductor in electrostatic equilibrium it equals ${ϵ}_0{\mathbf{E}}_{\mathrm{out}}\cdot \mathbf{n}$ for the normal pointing out of the conductor.

Two widely separated conducting spheres of radii $R_1,R_2$ connected by a thin wire have equal potentials, so a total charge $Q$ divides as

Two connected concentric spherical shells form one equipotential conductor. In the absence of charge in the inner cavity, all net charge lies on the exterior surface of the outer shell.

A neutral conducting sphere of radius $R$ in the field $E\hat{z}$ has exterior potential and induced surface chargeThe surface integral of $\sigma$ is zero.

Electrostatic energy can be written as one half the charge-potential integral or epsilon-zero over two times the electric-field energy integral.

A first spherical shell with charge $q$ followed by shells of charges $2(-1{)}^{n+1}q$ leaves enclosed charge $(-1{)}^{n+1}q$ after each shell. Gauss's law therefore gives the same squared electric field $q^2/(16{\pi }^2{ϵ}_0^2{r}^4)$ in every gap outside the first radius. Integrating the electrostatic energy density over all space gives $W=q^2/(8\pi {ϵ}_0{r}_1)$, independent of the other shell radii.

A thin spherical shell of radius $a$ carrying total charge $Q$ has surface potentialand electrostatic self-energy

For distinct point charges $q_i$ at positions $r_i$, the electrostatic potential energy isWhen some charges are fixed, the terms depending on a movable charge form its potential energy in their electric potential.

For coaxial cylinders of radii $a<b$ and length $L\gg b$, carrying charges per unit length $\pm \lambda$,The field energy is $U={\lambda }^{2}L\log (b/a)/(4\pi {ϵ}_0)=QV/2$.

The electric dipole moment is the integral of position weighted by charge density.

For a localized charge and current distribution satisfying charge conservation from Maxwell equations,

An electric dipole is a pair of equal and opposite charges in a small separation limit with their charge-times-separation vector held fixed.

Two point dipoles separated by $\mathbf{r}$ have interaction proportional to

For a localized charge distribution, the far electric potential is an inverse-radius expansion whose first terms are the total charge monopole, the electric dipole moment, and the electric quadrupole moment.

An electric quadrupole is a charge distribution whose total charge and electric dipole moment vanish while its second charge moment does not. Its potential decays as $r^{-3}$.

For charges $-Q,NQ,-MQ$ at $z=d,0,-d$, respectively,The monopole vanishes when $N=M+1$, the dipole vanishes when $M=1$, and both vanish when $(N,M)=(2,1)$.

Subject to $N=M+1$, keeping $Qd$ fixed as $d\to 0$ gives a finite point-dipole limit when $M\ne 1$. Keeping $Q{d}^2$ fixed gives a finite pure-quadrupole limit only when $M=1$; otherwise the dipole diverges.

For charges $-Q,2Q,-Q$ at $z=d,0,-d$, the exact force on a charge $-Q$ at $(x,0,0)$ isIt points toward the origin for every nonzero $x$.