Theoretical and Computational Chemistry

Spin State Ordering in Metal-Based Compounds Using the Localized Active Space Self-Consistent Field Method


Quantitatively accurate calculations for spin state ordering in transition-metal complexes typically demand a robust multiconfigurational treatment. The poor scaling of such methods with increasing size makes them impractical for large, strongly correlated systems. Density matrix embedding theory (DMET) is a fragmentation approach that can be used to specifically address this challenge. The single-determinantal bath framework of DMET is applicable in many situations, but it has been shown to perform poorly for molecules characterized by strong correlation when a multiconfigurational self-consistent field solver is used. To ameliorate this problem, the localized active space self-consistent field (LASSCF) method was recently described. In this work, LASSCF is applied to predict spin state energetics in mono- and di-iron systems and we show that the model offers an accuracy equivalent to CASSCF but at a substantially lower computational cost. Performance as a function of basis set and active space is also examined.


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Supplementary material

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LASSCFSpin 071919 SI ChemRxiv