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Lessons on O2 and NO bonding to heme from ab initio multireference/multiconfiguration and DFT calculations

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Abstract

This commentary focuses on the conceptual interpretation of the bonding of O2 and NO to heme in oxyheme and nitrosylheme complexes, using high-level ab initio complete active space self-consistent field (CASSCF)/molecular mechanical (MM), gas-phase CASSCF, and CASSCF followed by second-order perturbation theory (CASPT2) calculations as well as density functional theory (DFT) calculations. The commentary shows that expanding the complex multiconfigurational (MC) wave functions into valence bond (VB)-type configurations based on localized orbitals provides significant insight into bonding and precise definitions of oxidation states. Furthermore, the VB “reading” of the wave function unifies the descriptions of DFT and MC theories, reconciling controversies and surprises. In so doing, we demonstrate the impact of the protein bulk polarity and its hydrogen-bonding capability on the bonding. The insight provided by “reading” the VB content of the MC wave functions highlights the potential of this approach as a general paradigm in future computational bioinorganic chemistry. A great deal of insight lies in this road.

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Abbreviations

CASPT2:

Complete active space self-consistent field followed by second-order perturbation theory

CASSCF:

Complete active space self-consistent field

CASSCF(g):

Gas-phase CASSCF

CI:

Configuration interaction

CSF:

Configuration state function

DFT:

Density functional theory

GVB:

Generalized valence bond

Hb:

Hemoglobin

HO:

Heme oxygenase

Mb:

Myoglobin

MM:

Molecular mechanics

MR/MC:

Multireference/multiconfiguration

NOS:

Nitric oxide synthase

Por:

Porphine

QM:

Quantum mechanical

SAC:

Symmetry-adapted cluster

TCSCF:

Two-configuration self-consistent field

VB:

Valence bond

WFT:

Wave function theory

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Acknowledgment

S.S. is supported by an ISF grant (53/09).

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Authors and Affiliations

  1. Institute of Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, Hebrew University, 91904, Jerusalem, Israel

    Sason Shaik & Hui Chen

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  1. Sason Shaik
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  2. Hui Chen
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Correspondence to Sason Shaik.

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Dedicated to Björn O. Roos, whose untimely death is a great loss to science.

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Shaik, S., Chen, H. Lessons on O2 and NO bonding to heme from ab initio multireference/multiconfiguration and DFT calculations. J Biol Inorg Chem 16, 841–855 (2011). https://doi.org/10.1007/s00775-011-0763-1

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