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Para-hydrogen raser delivers sub-millihertz resolution in nuclear magnetic resonance

Nature Physics volume 13, pages 568–572 (2017)Cite this article

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Abstract

The precision of nuclear magnetic resonance spectroscopy1 (NMR) is limited by the signal-to-noise ratio, the measurement time Tm and the linewidth Δν = 1/(πT2). Overcoming the T2 limit is possible if the nuclear spins of a molecule emit continuous radio waves. Lasers2,3 and masers4,5,6,7,8,9,10,11,12,13 are self-organized systems which emit coherent radiation in the optical and micro-wave regime. Both are based on creating a population inversion of specific energy states. Here we show continuous oscillations of proton spins of organic molecules in the radiofrequency regime (raser5). We achieve this by coupling a population inversion created through signal amplification by reversible exchange (SABRE)14,15,16 to a high-quality-factor resonator. For the case of 15N labelled molecules, we observe multi-mode raser activity, which reports different spin quantum states. The corresponding 1H-15N J-coupled NMR spectra exhibit unprecedented sub-millihertz resolution and can be explained assuming two-spin ordered quantum states. Our findings demonstrate a substantial improvement in the frequency resolution of NMR.

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Figure 1: The liquid-state molecular raser.
Figure 2: Maser oscillation and SABRE spectrum of 15N labelled acetonitrile.
Figure 3: Maser oscillations of 15N labelled pyridine.
Figure 4: Spectral analysis of 15N pyridine raser signal.

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Acknowledgements

S.A. thanks the late C. H. Townes for inspiring discussions in Berkeley during autumn 2011. The authors gratefully acknowledge excellent technical assistance and financial support from S. van Waasen, R. Eichel and A. Schwaitzer from the Jülich Research Center and P. Schleker from RWTH Aachen University for help with respect to SABRE chemistry. Furthermore, we would like to thank I. Kalf for supplying deuterated pyridine, and greatly acknowledge J. A. Reimer from UC Berkeley for inspiring discussions and corrections.

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Authors and Affiliations

  1. Institute of Energy and Climate Research—Fundamental Electrochemistry (IEK-9), Forschungszentrum Jülich GmbH, D-52425 Jülich, Germany

    Martin Suefke

  2. Institut für Technische Chemie und Makromolekulare Chemie (ITMC), RWTH Aachen University, D-52056 Aachen, Germany

    Sören Lehmkuhl, Alexander Liebisch, Bernhard Blümich & Stephan Appelt

  3. Central Institute for Engineering, Electronics and Analytics—Electronic Systems (ZEA-2), Forschungszentrum Jülich GmbH, D-52425 Jülich, Germany

    Stephan Appelt

Authors
  1. Martin Suefke
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  2. Sören Lehmkuhl
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  3. Alexander Liebisch
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  4. Bernhard Blümich
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  5. Stephan Appelt
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Contributions

M.S. built the hardware for EHQE-NMR and para-hydrogen technology, performed experiments, and wrote software for data analysis. S.L. prepared optimized SABRE samples and conducted experiments. A.L. performed experiments and analysed experimental results. B.B. provided laboratory and experimental facilities and creative input. S.A. supervised the project, performed experiments, analysed experimental results, developed the theoretical framework and wrote software for simulation of NMR spectra. M.S., S.L., A.L., B.B. and S.A. wrote the paper.

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Correspondence to Martin Suefke.

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The authors declare no competing financial interests.

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Suefke, M., Lehmkuhl, S., Liebisch, A. et al. Para-hydrogen raser delivers sub-millihertz resolution in nuclear magnetic resonance. Nature Phys 13, 568–572 (2017). https://doi.org/10.1038/nphys4076

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