TY - JOUR
T1 - Spin-State Ordering in Metal-Based Compounds Using the Localized Active Space Self-Consistent Field Method
AU - Pandharkar, Riddhish
AU - Hermes, Matthew R.
AU - Cramer, Christopher J.
AU - Gagliardi, Laura
N1 - Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/9/19
Y1 - 2019/9/19
N2 - 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 that of CASSCF but at a substantially lower computational cost. Performance as a function of basis set and active space is also examined.
AB - 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 that of 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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U2 - 10.1021/acs.jpclett.9b02077
DO - 10.1021/acs.jpclett.9b02077
M3 - Article
C2 - 31429583
AN - SCOPUS:85072508894
SN - 1948-7185
VL - 10
SP - 5507
EP - 5513
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 18
ER -