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Title: 27AlNMR chemical shift of Al(OH)$$^{-}_{4}$$ calculated from first principles: Assessment of error cancellation in chemically distinct reference and target systems

Abstract

Predicting accurate nuclear magnetic resonance chemical shieldings relies upon cancellation of different types of errors between the theoretically calculated shielding constant of the analyte of interest and the reference. Often, the intrinsic error in computed shieldings due to basis sets, approximations in the Hamiltonian, description of the wave function, and dynamic effects is nearly identical between the analyte and reference, yet if the electronic structure or sensitivity to local environment differs dramatically, this cannot be taken for granted. Detailed prior work has examined the octahedral trivalent cation Al(H2O)$$^{3+}_{6}$$, accounting for ab initio intrinsic errors. However, the use of this species as a reference for the chemically distinct tetrahedral anion Al(OH)$$^{-}_{4}$$ requires an understanding of how these errors cancel, in order to define the limits of accurately predicting 27Al chemical shielding in Al(OH)$$^{-}_{4}$$. In this work, we estimate the absolute shielding of the 27Al nucleus in Al(OH)$$^{-}_{4}$$ at the coupled cluster level (515.1± 5.3 ppm). Shielding sensitivity to the choice of method approximation and atomic basis sets used has been evaluated. Solvent and thermal effects are assessed through ensemble averaging techniques using ab-initio molecular dynamics. The contribution of each type of intrinsic error is assessed for the Al(H2O)$$^{3+}_{6}$$ and Al(OH)$$^{-}_{4}$$ ions, revealing significant differences that fundamentally hamper the ability to accurately calculate the 27Al chemical shift of Al(OH)$$^{-}_{4}$$ from first principles.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]
  1. Washington State Univ., Pullman, WA (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. Washington State Univ., Pullman, WA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Interfacial Dynamics in Radioactive Environments and Materials (IDREAM); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1618421
Report Number(s):
PNNL-SA-150302
Journal ID: ISSN 0021-9606
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 152; Journal Issue: 13; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Martinez-Baez, Ernesto, Feng, Rulin, Pearce, Carolyn I., Schenter, Gregory K., and Clark, Aurora E. 27AlNMR chemical shift of Al(OH)$^{-}_{4}$ calculated from first principles: Assessment of error cancellation in chemically distinct reference and target systems. United States: N. p., 2020. Web. doi:10.1063/1.5144294.
Martinez-Baez, Ernesto, Feng, Rulin, Pearce, Carolyn I., Schenter, Gregory K., & Clark, Aurora E. 27AlNMR chemical shift of Al(OH)$^{-}_{4}$ calculated from first principles: Assessment of error cancellation in chemically distinct reference and target systems. United States. doi:https://doi.org/10.1063/1.5144294
Martinez-Baez, Ernesto, Feng, Rulin, Pearce, Carolyn I., Schenter, Gregory K., and Clark, Aurora E. Wed . "27AlNMR chemical shift of Al(OH)$^{-}_{4}$ calculated from first principles: Assessment of error cancellation in chemically distinct reference and target systems". United States. doi:https://doi.org/10.1063/1.5144294. https://www.osti.gov/servlets/purl/1618421.
@article{osti_1618421,
title = {27AlNMR chemical shift of Al(OH)$^{-}_{4}$ calculated from first principles: Assessment of error cancellation in chemically distinct reference and target systems},
author = {Martinez-Baez, Ernesto and Feng, Rulin and Pearce, Carolyn I. and Schenter, Gregory K. and Clark, Aurora E.},
abstractNote = {Predicting accurate nuclear magnetic resonance chemical shieldings relies upon cancellation of different types of errors between the theoretically calculated shielding constant of the analyte of interest and the reference. Often, the intrinsic error in computed shieldings due to basis sets, approximations in the Hamiltonian, description of the wave function, and dynamic effects is nearly identical between the analyte and reference, yet if the electronic structure or sensitivity to local environment differs dramatically, this cannot be taken for granted. Detailed prior work has examined the octahedral trivalent cation Al(H2O)$^{3+}_{6}$, accounting for ab initio intrinsic errors. However, the use of this species as a reference for the chemically distinct tetrahedral anion Al(OH)$^{-}_{4}$ requires an understanding of how these errors cancel, in order to define the limits of accurately predicting 27Al chemical shielding in Al(OH)$^{-}_{4}$. In this work, we estimate the absolute shielding of the 27Al nucleus in Al(OH)$^{-}_{4}$ at the coupled cluster level (515.1± 5.3 ppm). Shielding sensitivity to the choice of method approximation and atomic basis sets used has been evaluated. Solvent and thermal effects are assessed through ensemble averaging techniques using ab-initio molecular dynamics. The contribution of each type of intrinsic error is assessed for the Al(H2O)$^{3+}_{6}$ and Al(OH)$^{-}_{4}$ ions, revealing significant differences that fundamentally hamper the ability to accurately calculate the 27Al chemical shift of Al(OH)$^{-}_{4}$ from first principles.},
doi = {10.1063/1.5144294},
journal = {Journal of Chemical Physics},
number = 13,
volume = 152,
place = {United States},
year = {2020},
month = {4}
}

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