Zero-field J-spectroscopy of quadrupolar nuclei.

Picazo-Frutos, Román; Sheberstov, Kirill F; Blanchard, John W; Van Dyke, Erik; Reh, Moritz; Sjoelander, Tobias; Pines, Alexander; Budker, Dmitry et al. · Nat Commun · 2024

basic_science · Level V

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Abstract

Zero- to ultralow-field nuclear magnetic resonance (ZULF NMR) allows molecular structure elucidation via measurement of electron-mediated spin-spin J-couplings. This study examines zero-field J-spectra from molecules with quadrupolar nuclei, exemplified by solutions of various isotopologues of ammonium cations. The spectra reveal differences between various isotopologues upon extracting precise J-coupling values from pulse-acquire measurements. A primary isotope effect, <math xmlns="http://www.w3.org/1998/Math/MathML"><mo>△</mo> <mi>J</mi> <mo>=</mo> <mfenced> <mrow> <msub><mrow><mi>γ</mi></mrow> <mrow><msup><mrow></mrow> <mrow><mn>14</mn></mrow> </msup> <mi>N</mi></mrow> </msub> <mo>/</mo> <msub><mrow><mi>γ</mi></mrow> <mrow><msup><mrow></mrow> <mrow><mn>15</mn></mrow> </msup> <mi>N</mi></mrow> </msub> </mrow> </mfenced> <msub><mrow><mi>J</mi></mrow> <mrow><msup><mrow></mrow> <mrow><mn>15</mn></mrow> </msup> <mi>N</mi> <mi>H</mi></mrow> </msub> <mo>-</mo> <msub><mrow><mi>J</mi></mrow> <mrow><msup><mrow></mrow> <mrow><mn>14</mn></mrow> </msup> <mi>N</mi> <mi>H</mi></mrow> </msub> <mo>≈</mo> <mo>-</mo> <mn>58</mn></math> mHz, is deduced by analysis of the proton-nitrogen J-coupling ratios. This study points toward further experiments with symmetric cations containing quadrupolar nuclei, promising applications in biomedicine, energy storage, and benchmarking quantum chemistry calculations.