Importance of many body effects in the kernel of hemoglobin for ligand binding

Abstract

We propose a mechanism for binding of diatomic ligands to heme based on a dynamical orbital selection process. This scenario may be described as bonding determined by local valence fluctuations. We support this model using linear-scaling first-principles calculations, in combination with dynamical mean-field theory, applied to heme, the kernel of the hemoglobin metalloprotein central to human respiration. We find that variations in Hund's exchange coupling induce a reduction of the iron 3d density, with a concomitant increase of valence fluctuations. We discuss the comparison between our computed optical absorption spectra and experimental data, our picture accounting for the observation of optical transitions in the infrared regime, and how the Hund's coupling reduces, by a factor of five, the strong imbalance in the binding energies of heme with CO and O_2 ligands.

arXiv comment5 pages, 4 figures. Supplementary material 12 pages, 5 figures. This version (v2) matches that accepted for Physical Review Letters on 31 January 2013

References in corpus (9)

• Density functional theory in transition-metal chemistry: a self-consistent Hubbard U approach
• Janus-faced influence of the Hund's rule coupling in strongly correlated materials
• Hubbard U and Hund's Exchange J in Transition Metal Oxides: Screening vs. Localization Trends from Constrained Random Phase Approximation
• Magnetism and Charge Dynamics in Iron Pnictides
• Hund's coupling key role in multi-orbital correlations
• Vanadium dioxide : A Peierls-Mott insulator stable against disorder
• Self consistent GW determination of the interaction strength: application to the iron arsenide superconductors
• Projector self-consistent DFT+U using non-orthogonal generalized Wannier functions
• Ligand Discrimination in Myoglobin from Linear-Scaling DFT+U

Cited by in corpus (12)

• Towards ab initio self-energy embedding theory in quantum chemistry
• Electrostatic considerations affecting the calculated HOMO-LUMO gap in protein molecules
• Density Functional plus Dynamical Mean-Field Theory of the Spin-Crossover Molecule Fe(phen)${}_2$(NCS)${}_2$
• Dynamical mean field theory algorithm and experiment on quantum computers
• Lazy skip lists, a new algorithm for fast hybridization-expansion quantum Monte Carlo
• Renormalization of myoglobin-ligand binding energetics by quantum many-body effects
• Many-body renormalisation of forces in f-electron materials
• Calculating DMFT forces in ab-initio ultrasoft pseudopotential formalism
• Dynamical Mean-Field Theory of Strongly Correlated Electron Systems
• Efficient Compression Of The Environment Of An Open Quantum System
• Quantum embedding for molecules using auxiliary particles -- The ghost Gutzwiller Ansatz
• Quantum states entanglement in hemoglobin molecule active center