 Solution

Direct exchange is a quantum-mechanical spin-dependent energy arising from the Coulomb interaction and the required antisymmetry of a two-electron state. It requires spatial overlap of the relevant orbitals. It is not the classical magnetic dipole force between two small magnets, and it can be much stronger than that force.

For an explicit fixed-orbital illustration, take orthonormal spatial orbitals $a,b$. Orthonormality means $⟨a|b⟩=0$; it does not require their spatial densities to occupy disjoint regions. The normalized spatial states areThe symmetric spatial state combines with the antisymmetric spin-one-half singlet state, and the antisymmetric spatial state combines with a symmetric spin-one-half triplet state, so that the complete fermionic state is antisymmetric.

For Coulomb potential $V_{12}=e^2/(4\pi \epsilon |{\mathbf{r}}_1-{\mathbf{r}}_2|)$, distinguish the direct electrostatic integral and exchange integral:The Coulomb exchange splitting of two orbitals givesThe repulsive Coulomb potential makes $K\ge 0$ in this model. Thus the triplet is favored when the orbitals have nonzero exchange overlap. Its antisymmetric spatial wavefunction suppresses close Electron encounters and reduces their repulsion. Since the Coulomb interaction contains no explicit spin operator, the spin dependence enters through the allowed spatial symmetry.

For dimensionless spin operators ${\mathbf{s}}_i={\mathbf{\sigma }}_i/2$, whose pair eigenvalues are $1/4$ in the triplet and $-3/4$ in the singlet, the same splitting is represented byThis explicitly states the sign convention: positive $K$ here favors parallel spins. A convention $H=J{\mathbf{s}}_1\cdot {\mathbf{s}}_2$ would instead have $J=-2K$.

In a crystal, direct exchange therefore depends sensitively on orbital extent, overlap and interatomic spacing. It often decreases rapidly as localized orbitals separate. The fixed-orbital example does not prove that every material must be ferromagnetic: orbital rearrangement and competing kinetic or virtual-hopping processes alter the singlet-triplet balance. In particular, antiferromagnetic superexchange through an intermediate ligand is a different mechanism and should not be confused with direct overlap exchange.