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  Converged Structural and Spectroscopic Properties for Refined QM/MM Models of Azurin

Schulz, C. E., van Gastel, M., Pantazis, D. A., & Neese, F. (2021). Converged Structural and Spectroscopic Properties for Refined QM/MM Models of Azurin. Inorganic Chemistry, 60(10), 7399-7412. doi:10.1021/acs.inorgchem.1c00640.

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592_ic1c00640_si_001.pdf (Supplementary material), 2MB
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 Creators:
Schulz, Christine E.1, Author           
van Gastel, Maurice2, Author           
Pantazis, Dimitrios A.1, Author           
Neese, Frank3, Author           
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1Research Group Pantazis, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541711              
2Research Group van Gastel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541713              
3Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541710              

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 Abstract: Blue copper proteins continue to challenge experiment and theory with their electronic structure and spectroscopic properties that respond sensitively to the coordination environment of the copper ion. In this work, we report state-of-the art electronic structure studies for geometric and spectroscopic properties of the archetypal “Type I” copper protein azurin in its Cu(II) state. A hybrid quantum mechanics/molecular mechanics (QM/MM) approach is used, employing both density functional theory (DFT) and coupled cluster with singles, doubles, and perturbative triples (CCSD(T)) methods for the QM region, the latter method making use of the domain-based local pair natural orbital (DLPNO) approach. Models of increasing QM size are employed to investigate the convergence of critical geometric parameters. It is shown that convergence is slow and that a large QM region is critical for reproducing the short experimental Cu–SCys112 distance. The study of structural convergence is followed by investigation of spectroscopic parameters using both DFT and DLPNO-CC methods and comparing these to the experimental spectrum using simulations. The results allow us to examine for the first time the distribution of spin densities and hyperfine coupling constants at the coupled cluster level, leading us to revisit the experimental assignment of the 33S hyperfine splitting. The wavefunction-based approach to obtain spin-dependent properties of open-shell systems demonstrated here for the case of azurin is transferable and applicable to a large array of bioinorganic systems.

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Language(s): eng - English
 Dates: 2021-03-032021-05-032021-05-17
 Publication Status: Published in print
 Pages: 14
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 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.inorgchem.1c00640
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Title: Inorganic Chemistry
  Abbreviation : Inorg. Chem.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 60 (10) Sequence Number: - Start / End Page: 7399 - 7412 Identifier: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669