The effect of relaxation on the symmetry of N.M.R. spectra

The effect of nuclear relaxation on the symmetry properties of N.M.R. spectra is examined in terms of the properties of the relaxation matrix elements R_ijkl . It is found that the symmetry relations R_ijkl = R_jilk = R_klij = Rlkij obtain for one or more dominant relaxation mechanisms under ‘extreme narrowing’ conditions. Further, the symmetry relation R_ijkl = R_{λi, λj, λk, λl} , where λ is a spin inversion operator, is shown to obtain for (a) only one dominant relaxation mechanism or (b) two dominant relaxation mechanisms which have the same commutation properties with λ. This latter symmetry relation does not obtain for two dominant relaxation mechanisms with the same order of spatial dependence and different commutation properties with λ. The effect of nuclear relaxation can therefore yield unsymmetrical first-order spectra; the application of this analysis to the determination of the absolute sign of the spin-spin coupling constants is proposed.