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, △J=γ14N/γ15NJ15NH−J14NH≈−58\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\ riangle J=\\left({\\gamma }_{{}^{14}{{{{{\\rm{N}}}}}}}/{\\gamma }_{{}^{15}{{{{{\\rm{N}}}}}}}\\right){J}_{{}^{15}{{{{{\\rm{N}}}}}}{{{{{\\rm{H}}}}}}}-{J}_{{}^{14}{{{{{\\rm{N}}}}}}{{{{{\\rm{H}}}}}}}\\approx -58$$\\end{document} 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.
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