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The 1H NMR signal of the methyl group of sodium acetate is shown to be a triplet in the anisotropic environment of stretched gelatin gel. The multiplet structure of the signal is due to the intra-methyl residual dipolar couplings. The relaxation properties of the spin system were probed by recording steady-state irradiation envelopes (‘z-spectra’). A quantum–mechanical model based on irreducible spherical tensors formed by the three magnetically equivalent spins of the methyl group was used to simulate and fit experimental z-spectra. The multiple parameter values of the relaxation model were estimated by using a Bayesian-based Markov chain Monte Carlo algorithm.

The supramolecular complex, H2@C60, represents a model of a quantum rotor in a nearly spherical box. In providing a real example of a quantum particle entrapped in a small space, the system cuts to the heart of many important and fundamental quantum mechanical issues. This review compares the predictions of theory of the quantum behaviour of H2 incarcerated in C60 with the results of infrared spectroscopy, inelastic neutron scattering and nuclear magnetic resonance. For H2@C60, each of these methods supports the quantization of translational motion of H2 and the coupling of the translational motion with rotational motion and provides insights to the factors leading to breaking of the degeneracies of states expected for a purely spherical potential. Infrared spectroscopy and inelastic neutron scattering experiments at cryogenic temperatures provide direct evidence of a profound quantum mechanical feature of H2 predicted by Heisenberg based on the Pauli principle: the existence of two nuclear spin isomers, a nuclear spin singlet (para-H2) and a nuclear triplet (ortho-H2). Nuclear magnetic resonance is capable of probing the local lattice environment of H2@C60 through analysis of the H2 motional effects on the ortho-H2 spin dynamics (para-H2, the nuclear singlet state, is NMR silent). In this review we will show how the information obtained by three different forms of spectroscopy join together with quantum theory to create a complementary and consistent picture which strikingly shows the intrinsically quantum nature of H2@C60.

Internuclear couplings between selected homonuclear spin pairs in a multiply-labelled spin system are determined by NMR spin echo experiments in the solid-state. The spin echoes are induced by an amplitude-modulated shaped pulse. The time shift in the echo modulation curve is treated by average Hamiltonian theory and verified by numerical simulation. The J-couplings may be estimated by experiments on samples spinning at the magic-angle, while the direct dipole–dipole couplings may be estimated by off-magic-angle spinning. The concept is tested on a uniformly 13C-enriched sample of l-histidine hydrochloride monohydrate.