Can Multiconfigurational Self-Consistent Field Theory and Density Functional Theory Correctly Predict the Ground State of Metal-Metal-Bonded Complexes?

Rebecca K. Carlson, Samuel O. Odoh, Stephen J. Tereniak, Connie C. Lu, Laura Gagliardi

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

The electronic structure of a diiron (FeFe) complex with strong metal-metal interaction and those of analogous complexes (CoCo, CoMn, CoFe, and FeMn) with much weaker metal-metal bonding are investigated with wave function-based methods and density functional theory. The delocalization and bonding between the metal centers in the diiron complex is only fully captured after inclusion of the complete set of 3d and 4d orbitals in the active space, a situation best suited for restricted active space (RAS) approaches. Truncation of the included set of 4d orbitals results in inappropriate localization of some 3d orbitals, incorrect description of the ground spin state as well as wrong spin state energetics, as compared to experiment. Using density functional theory, some local functionals are able to predict the correct ground spin states, and describe the chemical bonding and structural properties of all the metal-metal complexes considered in this work. In contrast, the introduction of some exact exchange results in increased localization of 3d orbitals and wrong spin state energetics, a situation that is particularly troublesome for the diiron complex.

Original languageEnglish (US)
Pages (from-to)4093-4101
Number of pages9
JournalJournal of Chemical Theory and Computation
Volume11
Issue number9
DOIs
StatePublished - Sep 8 2015

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Metal complexes
Ground state
Density functional theory
self consistent fields
Metals
density functional theory
ground state
orbitals
metals
metal-metal bonding
functionals
Coordination Complexes
Wave functions
Electronic structure
Structural properties
wave functions
inclusions
electronic structure
approximation
interactions

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Can Multiconfigurational Self-Consistent Field Theory and Density Functional Theory Correctly Predict the Ground State of Metal-Metal-Bonded Complexes? / Carlson, Rebecca K.; Odoh, Samuel O.; Tereniak, Stephen J.; Lu, Connie C.; Gagliardi, Laura.

In: Journal of Chemical Theory and Computation, Vol. 11, No. 9, 08.09.2015, p. 4093-4101.

Research output: Contribution to journalArticle

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AB - The electronic structure of a diiron (FeFe) complex with strong metal-metal interaction and those of analogous complexes (CoCo, CoMn, CoFe, and FeMn) with much weaker metal-metal bonding are investigated with wave function-based methods and density functional theory. The delocalization and bonding between the metal centers in the diiron complex is only fully captured after inclusion of the complete set of 3d and 4d orbitals in the active space, a situation best suited for restricted active space (RAS) approaches. Truncation of the included set of 4d orbitals results in inappropriate localization of some 3d orbitals, incorrect description of the ground spin state as well as wrong spin state energetics, as compared to experiment. Using density functional theory, some local functionals are able to predict the correct ground spin states, and describe the chemical bonding and structural properties of all the metal-metal complexes considered in this work. In contrast, the introduction of some exact exchange results in increased localization of 3d orbitals and wrong spin state energetics, a situation that is particularly troublesome for the diiron complex.

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