Efficient Multiconfigurational Quantum Chemistry Approach to Single-Ion Magnets Based on Density Matrix Embedding Theory

Abstract

Density matrix embedding theory (DMET) provides a systematic framework to combine low-level (e.g., Hartree–Fock approximation) and high-level correlated quantum chemistry methods to treat strongly correlated systems. In this work, we propose an efficient quantum embedding approach that combines DMET with the complete active space self-consistent field and subsequent state interaction treatment of spin–orbit coupling (CASSI-SO) and apply it to a theoretical description of single-ion magnets (SIMs). We have developed a novel regularized direct inversion of iterative subspace (R-DIIS) technique that ensures restricted open-shell Hartree–Fock converging to a physically correct ground state, which is found to be crucial for the efficacy of subsequent CASSI-SO calculation. The DMET+CASSI-SO approach can produce reliable zero-field splitting parameters in typical 3d-SIMs with dramatically reduced computational cost compared to its all-electron counterpart. This work therefore demonstrates the great potential of DMET-based multiconfigurational approaches for efficient ab initio study of magneto–structural correlations in complex molecular magnetic systems.