Spin-lattice relaxation of the methyl group protons in solids revisited: damped quantum rotation approach.

Proton spin-lattice relaxation of the methyl group in solids had been one of the most thoroughly addressed theoretical problems in nuclear magnetic resonance (NMR) spectroscopy, considered at different levels of sophistication. For systems with substantial quantum tunneling effects, several quantum mechanical treatments were reported, although in practical applications the quantum models were always augmented with or replaced by the classical jump model. However, the latter has recently proved invalid in the description of NMR line shape effects in variable-temperature spectra of hindered methyl groups, while the competing theory of damped quantum rotation (DQR) was shown to be adequate. In this work, the spin-lattice relaxation issue for the methyl protons is readdressed using the latter theory. The main outcome is that, while the existing formulas for the relaxation rates remain unchanged, the crucial parameter entering them, the correlation time of the relevant random process, need to be reinterpreted....