Two-site Hubbard dimer

Two localized orbitals coupled by hopping, with an on-site penalty for double occupancy. At two-electron filling the competition between hopping and local repulsion can be solved exactly within the finite basis. It gives a compact example of a molecular bonding crossover and electron correlation; it is not by itself a complete real-molecule binding curve.

At one electron per site and $U\gg |t|$, the low-energy singlet of a repulsive two-site Hubbard dimer mixes virtually with doubly occupied configurations. Its energy is $-4t^2/U$ to leading order, while the three triplets have no such shift. With dimensionless spin-half operators this yields the displayed effective antiferromagnetic Hamiltonian. Restoring angular-momentum operators with units of $\hslash$ requires the corresponding $1/{\hslash }^2$ in the spin product.

For real hopping $t$ and repulsion $U>0$, the covalent singlet and symmetric ionic state have relative Hamiltonian $\left(\begin{array}{cc}0& 2t\\ 2t& U\end{array}\right)$. The lower energy is $(U-\sqrt{U^2+16t^2})/2$, relative to the common one-electron energy. It approaches $-4t^2/U$ at small hopping, and its state continuously mixes covalent and ionic configurations.

A configuration with both electrons on one center, such as $aa$ or $bb$, in a two-center electronic basis. A coherent superposition of such configurations in a neutral molecule represents charge fluctuations; it does not imply a permanent classical ionic charge assignment.

For orthonormal orbitals $a,b$, the symmetric spatial state $C=(|ab⟩+|ba⟩)/\sqrt{2}$ multiplied by the antisymmetric spin singlet has one electron on each center and no double occupancy. The full state remains antisymmetric under fermion exchange.