 Solution

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.