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A. A. Barker authored a 1965 calculation of radial distribution functions for a proton–electron plasma. The associated Barker acceptance probability supplies a useful rule for equilibrium Markov chain Monte Carlo: if the probability-and-proposal ratio for a proposed move is $r$, accept with probability $r/(1+r)$. For reverse moves the ratio is $1/r$, so the acceptance probabilities have ratio $r$, giving detailed balance. The rule connects a microscopic sampling decision with the desired equilibrium distribution.^[ref]

Author credited under these initials on the 1965 Monte Carlo method plasma paper Monte Carlo Calculations of the Radial Distribution Functions for a Proton-Electron Plasma by A. A. Barker. The initials are not expanded because an exact identity beyond the publication credit has not been established here. University of Adelaide thesis addendum identifying the 1965 publication.

For a classical monatomic homogeneous fluid with pairwise central pair potential $v(r)$, the mean interaction energy is one half the sum over neighbours of a tagged particle. Using the radial distribution function gives the displayed formula; the factor one half prevents counting each pair twice. The kinetic term follows from the equipartition theorem. Its use requires the relevant integral to exist and a thermodynamic state specified by number density and temperature. Quantum kinetic contributions, many-body forces and internal molecular modes require modifications.

Spatial homogeneity makes $\rho$ independent of position and makes the two-particle number density depend only on the separation. Isotropy removes its directional dependence. ConsequentlyHere $g_2$ is a radial distribution function, with the finite-$N$ normalization inherited from a; statistical independence is unnecessary. In particular, the translated pair in c has separation $\mathbf{R}$ for every $s$, so its $s$ integral is simply ${\rho }^2{g}_2(R,t)$.

Isotropy of the random velocity $\mathbf{c}=\mathbf{v}-\mathbf{u}$ makes its second velocity moment proportional to the identity. Taking its trace fixes the proportionality constant:Thus $\theta$ is the one-component random velocity variance; for unit mass in thermal equilibrium, $\theta =k_{B}T$. A Maxwell-Boltzmann velocity distribution is not required for the pressure tensor to be isotropic.

For the interaction contribution, the angular integral is $\int d\Omega {\hat{R}}_i{\hat{R}}_j=(4\pi /3){\delta }_{ij}$, by isotropy and its trace. With $d^{3}R=R^{2}dRd\Omega$, c becomesCombining the two pressure tensors gives the virial pressure from pair correlations:For a repulsive pair potential, the outward radial force is $-{\varphi }^{\prime }(R)\ge 0$. Since $g_2\ge 0$, the second term in $p$ is nonnegative, and positive when occupied separations feel nonzero repulsion. It expresses additional momentum transfer through interactions. The displayed integral assumes a differentiable pair potential and convergence; a hard core requires a contact formula or a limiting argument.

The radial distribution function is the conditional number density of neighbors at separation $r$, divided by the bulk number density $n$. In an isotropic three-dimensional liquid, the mean number in a thin spherical shell is $dN=4\pi n{r}^{2}g(r)dr$. Strong short-range repulsion makes $g(r)$ very small inside the effective particle core. A first maximum marks the nearest-neighbor coordination shell. More distant shells give weaker oscillations, which decay toward $g(r)=1$ as long-range positional correlations disappear. A typical simple liquid has no indefinitely repeated sharp lattice peaks.

The static structure factor measured by diffraction is related to the Fourier transform of $g(r)-1$. Thus the broad diffraction maxima of a liquid and the damped real-space coordination shells describe the same short-range organization.

Structure through pair correlations. For a homogeneous isotropic monatomic liquid of number density $n=N/V$, the radial distribution function $g(r)$ is defined byIt compares the conditional density around a tagged particle with the bulk density. A repulsive core makes close neighbours unlikely; a first peak identifies a preferred coordination shell, and damped peaks at larger radii describe short-range order. Far away, $g(r)\to 1$ in the bulk limit. Unlike a crystal, an ordinary liquid has no indefinitely repeated positional order. An ideal uncorrelated gas has $g(r)=1$ away from the tagged particle. The shell factor $4\pi r^2$ must not be confused with $g(r)$ itself.

The same pair structure enters the static structure factor measured through scattering. In the bulk isotropic convention,Thus real-space coordination and reciprocal-space scattering peaks describe the same correlations.

Energy from the structure. If interactions are sums of a central pair potential $v(r)$, the equipartition theorem gives the classical kinetic energy $3N{k}_{B}T/2$. Count the interaction of a tagged particle with its neighbours and divide by two to avoid counting each pair twice. The pair-correlation expression for internal energy isThis makes structure thermodynamically useful: short-distance repulsion and the attractive region contribute with different weights. Additional internal molecular modes or many-body interactions require extra terms. The formula is a classical bulk pair-potential result, not a universal energy formula for every liquid.

Pressure and the dilute expansion. The mechanical virial theorem relates the pair forces to pressure. The virial pressure from pair correlations isAt low density, $g(r)\simeq e^{-\beta v(r)}$, giving the virial expansionThe second virial coefficient has units of volume per particle; higher coefficients encode additional cluster correlations. A hard-sphere exclusion diameter $d$ gives $B_2=2\pi d^3/3>0$. Attractions contribute negative terms and can make $B_2$ negative. Although the pair-correlation formulas can describe a dense liquid when its actual $g(r)$ is known, truncating the virial series after a few terms is normally a dilute-fluid approximation. It should not be silently extrapolated through condensation or into a dense liquid.

The spatial marginal $n_2=\int f_2{d}^{3}v{d}^3{v}_{\star }$ of a number-normalized two-particle distribution function. It counts ordered distinct pairs, so its integral over both positions is $N(N-1)$. Exchange symmetry gives $n_2(\mathbf{x},{\mathbf{x}}_{\star })=n_2({\mathbf{x}}_{\star },\mathbf{x})$. In a homogeneous isotropic fluid it is $n^{2}g(|{\mathbf{x}}_{\star }-\mathbf{x}|)$, where $g$ is the radial distribution function.

For a differentiable central pair potential in a classical homogeneous three-dimensional fluid, the mechanical virial theorem gives the displayed pressure. The radial distribution function accounts for the probability of each pair separation. In the dilute limit, $g(r)=e^{-v(r)/(k_{B}T)}+O(n)$, and integration by parts yields $B_2(T)=-2\pi {\int }_0^{\infty }[e^{-v(r)/(k_{B}T)}-1]r^{2}dr$. Thus the second virial coefficient controls $p/(n{k}_{B}T)=1+B_{2}n+\cdots$. A few virial terms are a low-density approximation, not generally a converged description of a dense liquid. A discontinuous hard core needs its contact form or a limiting argument.