Spin-Pure Stochastic-CASSCF via GUGA-FCIQMC Applied to Iron-Sulfur Clusters

In this work, we demonstrate how to efficiently compute the one- and two-body reduced density matrices within the spin-adapted full configuration interaction quantum Monte Carlo (FCIQMC) method, which is based on the graphical unitary group approach (GUGA). This allows us to use GUGA-FCIQMC as a spin-pure configuration interaction (CI) eigensolver within the complete active space self-consistent field (CASSCF) procedure and hence to stochastically treat active spaces far larger than conventional CI solvers while variationally relaxing orbitals for specific spin-pure states. We apply the method to investigate the spin ladder in iron-sulfur dimer and tetramer model systems. We demonstrate the importance of the orbital relaxation by comparing the Heisenberg model magnetic coupling parameters from the CASSCF procedure to those from a CI-only (CASCI) procedure based on restricted open-shell Hartree-Fock orbitals. We show that the orbital relaxation differentially stabilizes the lower-spin states, thus enlarging the coupling parameters with respect to the values predicted by ignoring orbital relaxation effects. Moreover, we find that, while CASCI results are well fit by a simple bilinear Heisenberg Hamiltonian, the CASSCF eigenvalues exhibit deviations that necessitate the inclusion of biquadratic terms in the model Hamiltonian.

Automated summary

This work demonstrates efficiently computing reduced density matrices in spin-adapted full configuration interaction quantum Monte Carlo method, and using it as a spin-pure CI eigensolver within the CASSCF procedure, highlighting the importance of orbital relaxation. The method is applied to investigate spin ladder systems and shows the stabilization of lower-spin states through orbital relaxation and deviations in CASSCF eigenvalues that require the inclusion of biquadratic terms in the model Hamiltonian.