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Scalar couplings between covalently bound nuclear spins are a ubiquitousfeature in nuclear magnetic resonance (NMR) experiments, imparting valuableinformation to NMR spectra regarding molecular structure and conformation. Suchcouplings arise due to a second-order hyperfine interaction, and, in principle,the same mechanism should lead to scalar couplings between nuclear spins inunbound van der Waals complexes. Here, we report the first observation ofscalar couplings between nuclei in van der Waals molecules. Our measurementsare performed in a solution of hyperpolarized ${\rm ^{129}Xe}$ and pentane,using superconducting quantum interference devices to detect NMR in 10 mGfields, and are in good agreement with calculations based on density functionaltheory. van der Waals forces play an important role in many physical phenomena,and hence the techniques presented here may provide a new method for probingsuch interactions.

Observation of scalar nuclear spin-spin coupling in van der Waals molecules