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Density Matrix Embedding Theory-Based Multiconfigurational Quantum Chemistry Approach to Lanthanide Single-Ion
Yuhang Ai1, Ze-Wei Li1, Zhe-Bin Guan1
1Beijing National Laboratory for Molecular Sciences, Institute of Theoretical and Computational Chemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.
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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 multiconfigurational quantum chemistry method that combines the state-averaged complete active space self-consistent field (SA-CASSCF) approach with subsequent state interaction (SI) treatment of spin-orbit coupling (SOC), abbreviated as CASSCF-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 CASSCF-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 + CASSCF-SO approach to lanthanide SIM systems and further consider the dynamical correlation via multireference perturbation theory within the embedded cluster space. 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) wave functions, 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 treatment, with respect to its all-electron counterpart. We anticipate that this enhanced DMET-based multiconfigurational quantum chemistry methodology will significantly advance large-scale theoretical investigations of complex lanthanide systems.
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