The effect of a broad activation energy distribution on deuteron spin–lattice relaxation

Deuteron NMR spectra and spin–lattice relaxation were studied experimentally in zeolite NaY(2.4) samples containing 100 % or 200% of CD3OH or  CD3OD molecules of the total coverage of Na atoms in the temperature range 20 K – 150 K. The activation energies describing the methyl and hydroxyl motions show broad distributions. The relaxation data were interpreted by improving a recent model [Solid State Nucl. Magn. Reson. 49−50, 33–41 (2013)], in which the nonexponential relaxation curves are at first described by a sum of three exponentials with adjustable relaxation rates and weights. Then a broad distribution of activation energies (the mean activation energy A0 and the width s) was assumed for each essentially different methyl and hydroxyl position. The correlation times were calculated from the Arrhenius equation (containing the pre-exponential factor t0), individual relaxation rates computed and classified into three classes, and finally initial relaxation rates and weights for each class formed. These were compared with experimental data, motional parameters changed slightly and new improved rates and weights for each class calculated, etc. This method was improved by deriving for the deuterons of the A and E species methyl groups relaxation rates, which depend explicitly on the tunnel frequency wt. The temperature dependence of wt and of the low–temperature correlation time were obtained by using the solutions of the Mathieu equation for a threefold potential. These dependencies were included in the simulations and as the result sets of A0, s and t0 obtained, which describe the methyl and hydroxyl motions in different positions in zeolite.  </p

Acetone mobility in zeolite cages with new features in the deuteron NMR spectra and relaxation

We studied deuteron NMR spectra and spin−lattice relaxation of deuterated acetone-d6, adsorbed into zeolites NaX (1.3) and NaY(2.4) at 100% coverage of sodium cations. At temperatures roughly below 160 K the deuterons are localized and their NMR characteristics are determined by CD3 rotation and rotational oscillations of acetone molecules. In NaX the CD3 rotation and rotational oscillations about the twofold axis of acetone dominate the spectra below 100 K, while above it oscillations also about other axes become important. In NaY dominant features are related to methyl tunnelling and to a smaller extent to rigid acetones, before the rotational oscillations about twofold axis start to prevail above 40 K. The analysis of the strongly non-exponential magnetization recovery was done by applying the recently introduced method (Ylinen et al., 2015 [12]), improved here to take into account the limited fast recovery at the level crossings, 10% at ωt=ω0 and 28% at ωt=2ω0. At first the experimental recovery is fitted by three exponentials with adjustable weights and decay rates. Then these quantities are calculated from activation energy distributions and known expressions for the deuteron relaxation rate. In NaY two distinctly separate activation energy distributions were needed, the dominant one being very broad. The use of three distributions, two of them covering practically the same energies as the broad one, lead to a somewhat better agreement with experiment. In general the theoretical results agree with experiment within experimental scatter. As the final result the mean activation energies and widths are obtained for activation energy distributions.</div

Deuteron NMR relaxation, spectra, and evidence for the order-disorder phase transition in (ND4)2PtCl6

Deuteron NMR relaxation and spectra were studied at the resonance frequency of 46 MHz in polycrystalline (ND(4))(2)PtCl(6) between 300-5 K. The relaxation rate maximum near 50 K is about 53% smaller than the calculated maximum related to 120 degrees rotations about the threefold symmetry axes of the ammonium ion. The difference is explained by assuming for a N-D vector a total of 24 equilibrium directions, which in groups of six deviate from the nearest Pt-N vector by a certain angle Theta. So-called limited jumps between the directions of each group take place much more frequently than the large-angle rotations, thus rendering a fraction of the deuteron quadrupole coupling ineffective in relaxation. A motional model is presented, which takes into account both these motions simultaneously. A comparison with experimental data leads to Theta=26.0 degrees , in reasonable agreement with earlier neutron diffraction data. A sharp decrease found in the relaxation rate at the order-disorder phase transition temperature of 27.2 K is related to the fact that one of the six equilibrium directions becomes preferred. This leads to a formation of ordered domains, in which the active motion driving the relaxation is 120 degrees rotations. Two components in the spectra found below 55 K are related to domains (broad) and transition regions between domains (narrow). Reasons for the nonexponentiality observed below 20 K are discussed, the most likely explanation being that limited jumps dominate within transition regions and make the corresponding deuterons relax faster than those in domains