Restricted Open-Shell Cluster Mean-Field theory for Strongly Correlated Systems.

The cluster-based Mean Field method (cMF) and it is second order perturbative correction was introduced by Jiménez-Hoyos and Scuseria to reduce the cost of modeling strongly correlated systems by dividing an active space up into small clusters, which are individually solved in the mean-field presence of each other. In that work, clusters with unpaired electrons are treated by allowing the α and β orbitals to spin polarize. While that provided significant energetic stabilization, the resulting cMF wave function was spin-contaminated, making it difficult to use as a reference state for spin-pure post-cMF methods. In this work, we propose the Restricted Open-shell cMF (RO-cMF) method, extending the cMF approach to systems with open-shell clusters, while not permitting spin-polarization. While the resulting RO-cMF energies are necessarily higher in energy than the unrestricted orbital cMF, the new RO-cMF provides a simple reference state for post-cMF methods that recover the missing intercluster correlations. We provide a detailed explanation of the method, and report demonstrative calculations of exchange coupling constants for three systems: a di-iron complex, a dichromium complex, and a dimerized organic radical. We also report the first perturbatively corrected RO-cMF-PT2 results as well.