Symmetry Breaking and Broken Ergodicity in Full Configuration Interaction Quantum Monte Carlo

The initiator full configuration interaction quantum Monte Carlo method (i-FCIQMC) is applied to the binding curve of N2 in Slater-determinant Hilbert spaces formed of both canonical restricted Hartree–Fock (RHF) and symmetry-broken unrestricted Hartree–Fock (UHF) orbitals. By explicit calculation, we demonstrate that the technique yields the same total energy for both types of orbital but that as the bond is stretched, FCI expansions expressed in unrestricted orbitals are substantially more compact than their restricted counterparts and more compact than those expressed in split-localized orbitals. These unrestricted Hilbert spaces, however, become nonergodic toward the dissociation limit, and the total wave function may be thought of as the sum of two weakly coupled, spin-impure, functions whose energies are nonetheless very close to the exact energy. In this limit, it is a challenge for i-FCIQMC to resolve a spin-pure wave function. The use of unrestricted natural orbitals is a promising remedy for this problem, as their expansions are more strongly weighted toward lower excitations of the reference, and they provide stronger coupling to higher excitations than do UHF orbitals.