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A physicist associated with the Lennard-Jones potential.

Differentiate the Lennard-Jones potential. Its minimum satisfiesFor dilithium, the two wells consequently haveUnder an additional same-orbital, Hund-type exchange comparison, assign $(3.4,0.06)$ to the triplet and $(4.9,0.05)$ to the singlet: the lower-energy minimum is associated with the exchange-stabilized triplet state, as in part (a).

This assignment needs that extra orbital-parentage assumption. A scalar Lennard-Jones potential does not itself encode spin, and a common atomic dissociation limit does not specify a unique molecular electronic configuration or spatial symmetry. The two curves even cross at about $5.006$ bohr: neither lies below the other at every separation. Thus the minima and well depths are determined unambiguously; the spin labels are a conditional qualitative inference, rather than a unique consequence of the four supplied parameters. Neither “a triplet must always have a longer bond” nor a universal ordering of unrelated excited states is justified.

The minimum is at $r=1.878\mathring{\mathrm{A}}$ with depth $-0.250E_h$; the model is not a smooth physical potential at the cage centre. Put $s=R-r$ and $x=(B/s{)}^6$. Thenso $x=1/2$ is the minimum. ThereforewhileThe positive inverse-twelfth-power term mimics short-range overlap repulsion, while the negative inverse-sixth-power term mimics London dispersion force. These powers are used in the Lennard-Jones potential; they are not a microscopic derivation for an atom inside a carbon cage.

The relevant domain is $0\le r<R$. As the atom approaches the wall the model diverges positively, which is qualitatively sensible. However, the energy depends only on the nearest radial wall distance and omits all the other cage atoms. More decisively, $V^{\prime }(0)\ne 0$: a radial function of the Cartesian position must have zero first radial derivative at the centre to be differentiable there. The model produces a cusp and a nonvanishing directional force as the centre is approached. An off-centre minimum is not by itself forbidden, but this centre behaviour is inconsistent with a smooth symmetric cage potential.

With an attractive Lennard-Jones potential and $k_{B}T\ll ϵ$, a short run can remain trapped in an initial conformation or a metastable compact state. A distance trace may show a long apparently stationary segment, an initial collapse, or occasional jumps between local structures; its histogram depends on initialization and is not necessarily an equilibrium distribution. An extended start need not collapse on the available run length, and a compact start need not already be the global minimum.

Accepting only downhill moves would make this trapping worse and would not sample the specified finite-temperature canonical ensemble. The sketch should therefore label this trace as unequilibrated and avoid assigning its mean a thermodynamic interpretation.

The attractive part of the Lennard-Jones potential represents the London dispersion force between fluctuating atomic electric dipoles. The dipole-dipole interaction is proportional to $r^{-3}$; for nonpolar ground-state atoms its first-order expectation vanishes. In second-order perturbation theory, virtual excitations give a negative energy shift proportional to the square of that interaction, hence $-A/r^6$ with $A>0$. This applies at separations large compared with atomic size but small enough that electromagnetic retardation is negligible.

The repulsive term models the steep energy increase when closed electron shells overlap, involving the Pauli exclusion principle and increased electronic energy. The $r^{-12}$ power is an empirical convenient approximation, not a universal power derived from the exclusion principle; its being the square of $r^{-6}$ makes computation convenient. At still larger separations retardation changes the attractive asymptotics, outside this model.

Use the number-density virial expansion, following the density versus molar second virial convention, with $n=N/V$:Thus $B_2$ is the coefficient of the first density correction and has units of volume. With molar density instead, the molar coefficient is $N_A{B}_2$. For a classical pair potential $u(r)$,Attractive separations contribute negatively and short-range repulsion contributes positively. For inert-gas interactions the attractive contribution dominates at sufficiently low temperature, $B_2$ crosses zero at the Boyle temperature, and repulsion dominates above it.

The soft-core high-temperature second virial coefficient illustrates why the far-high-temperature tail depends on the model. A hard-core estimate $B_2\simeq b-a/(k_{B}T)$ tends to positive excluded volume $b$. A soft repulsive potential, such as the Lennard-Jones potential in the original diagram, allows a positive maximum followed by decay toward zero. The sign change is the main attraction-versus-repulsion feature; neither sketch should be interpreted as measured data for a specified gas. This classical, dilute-gas sketch omits low-temperature quantum-exchange corrections.^[ref]