Thursday, September 20, 2012

1H relaxation dispersion in solutions of nitroxide radicals: Effects of hyperfine interactions with 14N and 15N nuclei

Kruk, D., et al., 1H relaxation dispersion in solutions of nitroxide radicals: Effects of hyperfine interactions with 14N and 15N nuclei. J. Chem. Phys., 2012. 137(4): p. 044512-12.

1H relaxation dispersion of decalin and glycerol solutions of nitroxide radicals, 4-oxo-TEMPO-d16-15N and 4-oxo-TEMPO-d16-14N was measured in the frequency range of 10 kHz–20 MHz (for 1H) using STELAR Field Cycling spectrometer. The purpose of the studies is to reveal how the spin dynamics of the free electron of the nitroxide radical affects the proton spin relaxation of the solvent molecules, depending on dynamical properties of the solvent. Combining the results for both solvents, the range of translational diffusion coefficients, 10−9–10−11 m2/s, was covered (these values refer to the relative diffusion of the solvent and solute molecules). The data were analyzed in terms of relaxation formulas including the isotropic part of the electron spin – nitrogen spin hyperfine coupling (for the case of 14N and 15N) and therefore valid for an arbitrary magnetic field. The influence of the hyperfine coupling on 1H relaxation of solvent molecules depending on frequency and time-scale of the translational dynamics was discussed in detail. Special attention was given to the effect of isotope substitution (14N/15N). In parallel, the influence of rotational dynamics on the inter-molecular (radical – solvent) electron spin – proton spin dipole-dipole coupling (which is the relaxation mechanism of solvent protons) was investigated. The rotational dynamics is of importance as the interacting spins are not placed in the molecular centers. It was demonstrated that the role of the isotropic hyperfine coupling increases for slower dynamics, but it is of importance already in the fast motion range (10−9m2/s). The isotope effects is small, however clearly visible; the 1H relaxation rate for the case of 15N is larger (in the range of lower frequencies) than for 14N. It was shown that when the diffusion coefficient decreases below 5 × 10−11 m2/s electron spin relaxation becomes of importance and its role becomes progressively more significant when the dynamics slows done. As far as the influence of the rotational dynamics is concerned, it was show that this process is of importance not only in the range of higher frequencies (like for diamagnetic solutions) but also at low and intermediate frequencies.