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

Riddhish Pandharkar, Matthew R. Hermes, Christopher J. Cramer, Laura Gagliardi

Research output: Contribution to journalArticlepeer-review

5 Scopus citations

Abstract

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.

Original languageEnglish (US)
Pages (from-to)5507-5513
Number of pages7
JournalJournal of Physical Chemistry Letters
Volume10
Issue number18
DOIs
StatePublished - Sep 19 2019

Bibliographical note

Funding Information:
We thank Sina Chiniforoush, Hung Quam Pham, and Donald G. Truhlar for useful discussions. L.G. had useful discussion with Karin Fink and Christoph van Wüllen. This research is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences under Award DEFG02-17ER16362. Computer resources were provided by the Minnesota Supercomputing Institute at the University of Minnesota.

Publisher Copyright:
© 2019 American Chemical Society.

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