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The Mayer f-function measures how a pair potential changes a pair's Boltzmann factor relative to the noninteracting value one:It vanishes where $u=0$, lies between $-1$ and $0$ for repulsion, and is positive for attraction. Even an infinite hard-core potential energy produces the finite value $f=-1$. This is why expanding in Mayer f-functions handles a hard-sphere gas more naturally than a Taylor series in $u$. ^[ref]

For pairwise-additive potential energy $U={\sum }_{i<j}u(r_{ij})$, the exact identityturns the configurational part of the canonical partition function into a sum of products associated with pairs. Drawing one edge for each chosen factor $f(r_{ij})$ gives the graphs used in the cluster expansion. The second virial coefficient uses just one pair's relative-position integral, $B_2=-\frac{1}{2}\int f{d}^3\mathbf{r}$.

For the square-well toy pair potential in second virial coefficient, $f=-1$ in the core, $f=e^{1/T^{\ast }}-1$ in the attractive shell, and $f=0$ beyond it. Its positive plateau need not be small: low number density, rather than small $f$ at every separation, controls the dilute-gas approximation. The integral weights each plateau by spherical-shell volume; equal-looking unweighted areas on a plot of $f$ versus $r$ need not cancel in $B_2$.