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  A Joint Venture of Ab Initio Molecular Dynamics, Coupled Cluster Electronic Structure Methods, and Liquid-State Theory to Compute Accurate Isotropic Hyperfine Constants of Nitroxide Probes in Water

Sharma, B., Tran, V. A., Pongratz, T., Galazzo, L., Zhurko, I., Bordignon, E., et al. (2021). A Joint Venture of Ab Initio Molecular Dynamics, Coupled Cluster Electronic Structure Methods, and Liquid-State Theory to Compute Accurate Isotropic Hyperfine Constants of Nitroxide Probes in Water. Journal of Chemical Theory and Computation, 17(10), 6366-6386. doi:10.1021/acs.jctc.1c00582.

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605_ct1c00582_si_001.pdf (Supplementary material), 469KB
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Sharma, Bikramjit1, Author
Tran, Van Anh2, Author              
Pongratz, Tim3, Author
Galazzo, Laura4, Author
Zhurko, Irina5, Author
Bordignon, Enrica4, Author
Kast, Stefan M.3, Author
Neese, Frank2, Author              
Marx, Dominik1, Author
Affiliations:
1Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, 44780 Bochum, Germany, ou_persistent22              
2Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541710              
3Physikalische Chemie III, Technische Universität Dortmund, Otto-Hahn-Str. 4a, 44227 Dortmund, Germany, ou_persistent22              
4Faculty of Chemistry and Biochemistry, Ruhr University Bochum, 44780 Bochum, Germany, ou_persistent22              
5Laboratory of Nitrogen Compounds, N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, NIOCH SB RAS, 9 Lavrentiev Avenue, 630090, Novosibirsk, Russia, ou_persistent22              

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 Abstract: The isotropic hyperfine coupling constant (HFCC, Aiso) of a pH-sensitive spin probe in a solution, HMI (2,2,3,4,5,5-hexamethylimidazolidin-1-oxyl, C9H19N2O) in water, is computed using an ensemble of state-of-the-art computational techniques and is gauged against X-band continuous wave electron paramagnetic resonance (EPR) measurement spectra at room temperature. Fundamentally, the investigation aims to delineate the cutting edge of current first-principles-based calculations of EPR parameters in aqueous solutions based on using rigorous statistical mechanics combined with correlated electronic structure techniques. In particular, the impact of solvation is described by exploiting fully atomistic, RISM integral equation, and implicit solvation approaches as offered by ab initio molecular dynamics (AIMD) of the periodic bulk solution (using the spin-polarized revPBE0-D3 hybrid functional), embedded cluster reference interaction site model integral equation theory (EC-RISM), and polarizable continuum embedding (using CPCM) of microsolvated complexes, respectively. HFCCs are obtained from efficient coupled cluster calculations (using open-shell DLPNO-CCSD theory) as well as from hybrid density functional theory (using revPBE0-D3). Re-solvation of “vertically desolvated” spin probe configuration snapshots by EC-RISM embedding is shown to provide significantly improved results compared to CPCM since only the former captures the inherent structural heterogeneity of the solvent close to the spin probe. The average values of the Aiso parameter obtained based on configurational statistics using explicit water within AIMD and from EC-RISM solvation are found to be satisfactorily close. Using either such explicit or RISM solvation in conjunction with DLPNO-CCSD calculations of the HFCCs provides an average Aiso parameter for HMI in aqueous solution at 300 K and 1 bar that is in good agreement with the experimentally determined one. The developed computational strategy is general in the sense that it can be readily applied to other spin probes of similar molecular complexity, to aqueous solutions beyond ambient conditions, as well as to other solvents in the longer run.

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Language(s): eng - English
 Dates: 2021-06-112021-09-132021-10-12
 Publication Status: Published in print
 Pages: 21
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.jctc.1c00582
 Degree: -

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Title: Journal of Chemical Theory and Computation
  Abbreviation : J. Chem. Theory Comput.
Source Genre: Journal
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Publ. Info: Washington, D.C. : American Chemical Society
Pages: - Volume / Issue: 17 (10) Sequence Number: - Start / End Page: 6366 - 6386 Identifier: ISSN: 1549-9618
CoNE: https://pure.mpg.de/cone/journals/resource/111088195283832