Density Matrix Embedding Theory-Based Multi-Configurational Quantum Chemistry Approach to Lanthanide Single-Ion Magnets

Abstract: Accurate and efficient theoretical descriptions of lanthanide systems based on ab initio electronic structure theory remain highly challenging due to the complex interplay of strong electronic correlation and significant relativistic effects in 4f electrons. The composite multi-configurational quantum chemistry method, which combines the complete active space self-consistent field (CASSCF) approach with subsequent state interaction (SI) treatment of spin-orbit coupling (SOC), abbreviated as CASSI-SO, has emerged as the preferred method for ab initio studies of lanthanide systems. However, its widespread application is hindered by its substantial computational cost. Building on the success of integrating density-matrix embedding theory (DMET) with CASSI-SO in our previous theoretical study of 3d single-ion magnets (SIMs) (Ai, Sun, and Jiang, J. Phys. Chem. Lett. 2022, 13, 10627), we now extend the DMET+CASSI-SO approach to lanthanide SIM systems. We provide a detailed formulation of the regularized direct inversion of iterative subspace (R-DIIS) algorithm, which ensures obtaining physically correct restricted open-shell Hartree-Fock (ROHF) wavefunctions, a critical factor for the effectiveness of DMET. Additionally, we introduce the subspace R-DIIS (sR-DIIS) algorithm, which proves to be more efficient and robust for lanthanide systems. Using several representative lanthanide single-ion magnets (4f-SIMs) as test cases, we demonstrate the performance of these new algorithms and highlight the exceptional accuracy of the DMET+CASSI-SO approach. We anticipate that this enhanced DMET+CASSI-SO methodology will significantly advance large-scale theoretical investigations of complex lanthanide systems.