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DOE OSTI · 2521984

Projector‐Based Quantum Embedding Study of Iron Complexes

Waldrop, Jonathan M. [Ames Laboratory (AMES), Ames, IA (United States)] (ORCID:000000030442193X)·Panyala, Ajay [Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)]·Mejia‐Rodriguez, Daniel [Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)] (ORCID:0000000203502941)·Windus, Theresa L. [Ames Laboratory, and Iowa State Univ., Ames, IA (United States)]·Govind, Niranjan [Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Univ. of Washington, Seattle, WA (United States)]
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Abstract

Projection‐based embedding theory (PBET) is used to calculate and assess the challenging spin‐crossover energies for a selection of small Fe‐containing systems by embedding the metal center into the frozen potential of the ligands. MP2, CCSD, and CCSD(T) are embedded in potentials from the SCAN and r 2 SCAN functionals and compared with the canonical values for the constituent methods and previously reported reference values. Considering the PBET calculations as a correction for the underlying DFT, the embedding calculations are able to provided improvement for most cases. In some cases, the PBET methods are able to compensate for limitations in the wave function methods and produce results similar to more rigorous calculations from the literature. For the systems with spin‐crossover energies near zero, the current methodology fails to provide consistent improvement. In conclusion, the isolated recalculation of the electronic structure around the metal center when embedded into a DFT treatment of the ligand field shows promise as a pragmatic and lower cost treatment compared to the canonical treatment of the whole system of the difficult class of spin‐crossover complexes.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRYdensity functional theoryelectronic structure calculationsembeddingenergyquantum mechanics

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Waldrop, Jonathan M. [Ames Laboratory (AMES), Ames, IA (United States)] (ORCID:000000030442193X), Panyala, Ajay [Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)], Mejia‐Rodriguez, Daniel [Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)] (ORCID:0000000203502941), Windus, Theresa L. [Ames Laboratory, and Iowa State Univ., Ames, IA (United States)], Govind, Niranjan [Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Univ. of Washington, Seattle, WA (United States)]. 2025-01-29. Projector‐Based Quantum Embedding Study of Iron Complexes. https://doi.org/10.1002/jcc.70043

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