Fingerprints of damped quantum rotation observed in solid-state proton NMR spectra.

(1)H NMR spectra of the methyl group in an oriented crystal sample of methylmalonic acid with all three non-methyl protons replaced by deuterons are interpreted in terms of the damped quantum rotation (DQR) theory of NMR line shapes. The DQR approach offers a perfect theoretical reproduction of the observed spectra while the conventional Alexander-Binsch line-shape model shows evident defects in the present case. The temperature trends of the quantities characterizing the coherent and incoherent dynamics of the methyl group in the DQR approach (the effective tunnelling frequency and two coherence-damping rates) derived from the spectra are fairly reproduced using a model reported previously. The present findings provide further evidence of limitations to the validity of the common belief that molecular rate processes in condensed phases are necessarily classical.

The shape and information content of high-field solid-state proton NMR spectra of methyl groups.

The possible variation of the lineshape of the high-field 1H spectrum of methyl groups is explored by simulation and experiment. The spectrum of an isolated methyl group depends, apart from the orientation of the applied field B0 relative to the C3-axis of the group, on its rotational tunnel frequency vt and on its stochastic reorientation rate k. For quantitative analyses, the directional mobility of the C3-axis must also be taken into account. A distinct but frequently occurring case arises when the methyl groups come as pairs of magnetically equivalent close neighbours. For the experiments, single crystals of four compounds I-IV were grown that were isotopically substituted such that they contained protons only in the methyl positions. The crystal symmetry of all compounds I-IV allowed us to record spectra with all methyl groups being orientationally and otherwise equivalent. I, acetonitrile in deuterated hydroquinone, represents the case of a well-isolated methyl group with a "high" tunnel frequency vt. Its spectrum is (almost) independent of the temperature T. In II, monomethyl malonic acid, vt is comparable in size with the strength of the intramolecular dipolar H-H interaction. All seven theoretically expected lines in the 1H spectrum are clearly resolved in the spectra of II. vt can be inferred with an uncertainty of only +/- 300 Hz. vt(T) is found to possess a (flat) maximum near 40 K. Compound III, L-alanine, allows the study of the case of a methyl group with an extremely low, although nonzero tunnel frequency (vt approximately 3 kHz) while IV, dimethylglyoxime, represents the case of a close pair of equivalent methyl groups. Its spectrum reflects intriguing structural implications.