TY - JOUR
T1 - Quadrupolar 23Na+ NMR relaxation as a probe of subpicosecond collective dynamics in aqueous electrolyte solutions
AU - Chubak, Iurii
AU - Alon, Leeor
AU - Silletta, Emilia V.
AU - Madelin, Guillaume
AU - Jerschow, Alexej
AU - Rotenberg, Benjamin
N1 - Funding Information:
We would like to thank Dr. Seena Dehkharghani for the thoughtful discussions on the influence of temperature on water dynamics and NMR relaxation parameters and Dr. Antoine Carof for useful discussions on the modeling of quadrupolar NMR relaxation. This work was supported in part by the National Institutes of Health (NIH): grant no. R01EB026456 (G.M.). This project received funding from the European Research Council under the European Union’s Horizon 2020 research and innovation program (grant agreement no. 863473, B.R.). The authors acknowledge access to HPC resources from GENCI (grant no. A0110912966, B.R.), and A.J. wishes to acknowledge the HPC resources of NYU. A.J. acknowledges funding from the US National Science Foundation under award no. CHE2108205.
Publisher Copyright:
© 2023, The Author(s).
PY - 2023/12
Y1 - 2023/12
N2 - Nuclear magnetic resonance relaxometry represents a powerful tool for extracting dynamic information. Yet, obtaining links to molecular motion is challenging for many ions that relax through the quadrupolar mechanism, which is mediated by electric field gradient fluctuations and lacks a detailed microscopic description. For sodium ions in aqueous electrolytes, we combine ab initio calculations to account for electron cloud effects with classical molecular dynamics to sample long-time fluctuations, and obtain relaxation rates in good agreement with experiments over broad concentration and temperature ranges. We demonstrate that quadrupolar nuclear relaxation is sensitive to subpicosecond dynamics not captured by previous models based on water reorientation or cluster rotation. While ions affect the overall water retardation, experimental trends are mainly explained by dynamics in the first two solvation shells of sodium, which contain mostly water. This work thus paves the way to the quantitative understanding of quadrupolar relaxation in electrolyte and bioelectrolyte systems.
AB - Nuclear magnetic resonance relaxometry represents a powerful tool for extracting dynamic information. Yet, obtaining links to molecular motion is challenging for many ions that relax through the quadrupolar mechanism, which is mediated by electric field gradient fluctuations and lacks a detailed microscopic description. For sodium ions in aqueous electrolytes, we combine ab initio calculations to account for electron cloud effects with classical molecular dynamics to sample long-time fluctuations, and obtain relaxation rates in good agreement with experiments over broad concentration and temperature ranges. We demonstrate that quadrupolar nuclear relaxation is sensitive to subpicosecond dynamics not captured by previous models based on water reorientation or cluster rotation. While ions affect the overall water retardation, experimental trends are mainly explained by dynamics in the first two solvation shells of sodium, which contain mostly water. This work thus paves the way to the quantitative understanding of quadrupolar relaxation in electrolyte and bioelectrolyte systems.
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U2 - 10.1038/s41467-022-35695-3
DO - 10.1038/s41467-022-35695-3
M3 - Article
C2 - 36604414
AN - SCOPUS:85145645729
VL - 14
JO - Nature Communications
JF - Nature Communications
SN - 2041-1723
IS - 1
M1 - 84
ER -