Electronic landscape of the P-cluster of nitrogenase as revealed through many-electron quantum wavefunctions

Abstract

The electronic structure of the nitrogenase metal cofactors is central to nitrogen fixation. However, the P-cluster and iron molybdenum cofactor, each containing eight irons, have resisted detailed characterization of their electronic properties. Through exhaustive many-electron wavefunction simulations enabled by new theoretical methods, we report on the low-energy electronic states of the P-cluster in three oxidation states. The energy scales of orbital and spin excitations overlap, yielding a dense spectrum with features we trace to the underlying atomic states and recouplings. The clusters exist in superpositions of spin configurations with non-classical spin correlations, complicating interpretation of magnetic spectroscopies, while the charges are mostly localized from reorganization of the cluster and its surroundings. Upon oxidation, the opening of the P-cluster significantly increases the density of states, which is intriguing given its proposed role in electron transfer. These results demonstrate that many-electron simulations stand to provide new insights into the electronic structure of the nitrogenase cofactors.

arXiv comment23 pages, 5 figures

References in corpus (4)

• The density-matrix renormalization group in the age of matrix product states
• Ab Initio Quantum Chemistry using the Density Matrix Renormalization Group
• Low-energy spectrum of iron-sulfur clusters directly from many-particle quantum mechanics
• A spin-adapted Density Matrix Renormalization Group algorithm for quantum chemistry

Cited by in corpus (27)

• Recent developments in the PySCF program package
• Quantum algorithms for quantum chemistry and quantum materials science
• The Density Matrix Renormalization Group in Chemistry and Molecular Physics: Recent Developments and New Challenges
• Is there evidence for exponential quantum advantage in quantum chemistry?
• Emerging quantum computing algorithms for quantum chemistry
• Block2: a comprehensive open source framework to develop and apply state-of-the-art DMRG algorithms in electronic structure and beyond
• Low communication high performance ab initio density matrix renormalization group algorithms
• The chromium dimer: closing a chapter of quantum chemistry
• Quantum-centric Supercomputing for Materials Science: A Perspective on Challenges and Future Directions
• Ab Initio Full Cell GW+DMFT for Correlated Materials
• Toward Practical Quantum Embedding Simulation of Realistic Chemical Systems on Near-term Quantum Computers
• Correlation-consistent Gaussian basis sets for solids made simple
• Matrix product states with large sites
• Measuring Electron Correlation. The Impact of Symmetry and Orbital Transformations
• Rapid initial state preparation for the quantum simulation of strongly correlated molecules
• Legendre-spectral Dyson equation solver with super-exponential convergence
• The Effect of Geometry, Spin and Orbital Optimization in Achieving Accurate, Fully-Correlated Results for Iron-Sulfur Cubanes
• Fault-tolerant quantum algorithms for quantum molecular systems: A survey
• Cluster many-body expansion: a many-body expansion of the electron correlation energy about a cluster mean-field reference
• Expressibility of comb tensor network states (CTNS) for the P-cluster and the FeMo-cofactor of nitrogenase
• Unbiasing Fermionic Auxiliary-Field Quantum Monte Carlo with Matrix Product State Trial Wavefunctions
• Minimal matrix product states and generalizations of mean-field and geminal wavefunctions
• A full configuration interaction quantum Monte Carlo study of ScO, TiO and VO molecules
• Spin coupling is all you need: Encoding strong electron correlation in molecules on quantum computers
• Multireference protonation energetics of a dimeric model of nitrogenase iron-sulfur clusters
• Interpolating many-body wave functions for accelerated molecular dynamics on the near-exact electronic surface
• Quantum Machine Learning of Molecular Energies with Hybrid Quantum-Neural Wavefunction