Concept

Bjerrum length — where it appears

The distance at which two unit charges in a solvent interact with an energy equal to the thermal energy, 0.71 nanometres in water at room temperature. Charges closer than this are bound by electrostatics; farther apart, thermal motion wins.

Named by 2 essays across one field — each of them below, with the objects they name alongside it.

Also named here as counterion condensation, poisson boltzmann equation — the same set of essays touches all of them, so they are one junction rather than several.

$Most of a chain's counterions never leave it. The fraction of a charged rod's counterions lying within a distance r of it, against r in rod radii on a logarithmic axis, for a charge parameter ξ = 4.2 — the Bjerrum length of water, 0.7135 nm, over a charge spacing of 0.17 nm, which is DNA's. Each curve is the Poisson–Boltzmann solution for the rod at the centre of a cell of radius 10², 10⁴, 10⁶ rod radii, with its counterions checked to neutralise it exactly. Diluting the solution widens the cell by four decades at a time, and a counterion free to go anywhere in the cell ought to spread with it; instead each curve keeps a plateau near the rod whose height does not change. At the inflection of every curve the enclosed fraction is 0.762, which is Manning's 1 − 1/ξ, and the plateau sits there: 76 per cent of the counterions stay bound to the chain however dilute the solution, and only 24 per cent spread through it.$

The counterions that never leave the chain

Dilute a solution of DNA a million times and its counterions ought to scatter through the whole volume. Three quarters of them do not. A line of charges closer together than the Bjerrum length — 0.71 nm in water — holds on to its counterions however much room they are given, until the chain's charge is cut back to one per Bjerrum length, and every osmotic pressure, swelling gel and packed virus built from such chains is set by that length rather than by the chemistry.

fluids · Osmosis

Mean field always pushes; correlations pull. The pressure between two planes of equal charge with only their own counterions between them, against their separation, in units of the Gouy–Chapman length μ for the separation and 2πℓ_Bσ²kT for the pressure. The upper curve is the Poisson–Boltzmann result, solved from k·tan(kd/2) = 1: it is the density of counterions at the midplane and is positive at every separation, falling from the ideal-gas 2/d at contact to π²/d² far apart — 1.71 at 1μ, 0.290 at 4μ. The lower curve is the strong-coupling limit, 2/d − 1, which the same ions reach when their valence and the surface charge are high. It crosses zero at d = 2μ and is negative beyond, tending to −1: the two like-charged planes attract, and the separation 2μ is where they come to rest.

The like charges that pull together

Two surfaces carrying the same charge, with nothing between them but the ions that neutralise them, ought to repel, and the standard mean-field theory proves that they always do. With calcium or spermine as the counterions they attract, and come to rest a fraction of a nanometre apart. The mean field misses it because it averages the ions into a smooth cloud, and multivalent ions are too strongly repelled by each other to form one. Each keeps a patch of surface to itself, and the pressure between the plates becomes a single ion's business.

fluids · Osmosis

Named alongside it

The objects these essays reach for when they reach for this one.

Counterion condensation Electrostatics Osmotic pressure Poisson boltzmann equation Contact value theorem Correlation Coupling parameter Entropy Like charge attraction Mean-field theory Osmosis Polyelectrolyte

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