Longitudinal nuclear spin relaxation of ortho- and para-hydrogen dissolved in organic solvents

The longitudinal relaxation time of ortho-hydrogen (the spin isomer directly observable by NMR) has been measured in various organic solvents as a function of temperature. Experimental data are perfectly interpreted by postulating two mechanisms, namely intramolecular dipolar interaction and spin-rotation, with activation energies specific to these two mechanisms and to the solvent in which hydrogen is dissolved. This permits a clear separation of the two contributions at any temperature. Contrary to the self-diffusion coefficients at a given temperature, the rotational correlation times extracted from the dipolar relaxation contribution do not exhibit any definite trend with respect to solvent viscosity. Likewise, the spin-rotation correlation time obeys Hubbard's relation only in the case of hydrogen dissolved in acetone-d6, yielding in that case a spin-rotation constant in agreement with literature data. Concerning para-hydrogen, which is NMR-silent, the only feasible approach is to dissolve para-enriched hydrogen in these solvents and to follow the back-conversion of the para-isomer into the ortho-isomer. Experimentally, this conversion has been observed to be exponential, with a time constant assumed to be the relaxation time of the singlet state (the spin state of the para-isomer). A theory, based on intermolecular dipolar interactions, has been worked out for explaining the very large values of these relaxation times which appear to be solvent-dependent.