Deuteron NMR spin–lattice relaxation of NH 3D + ions in partially deuterated (NH 4) 2SnCl 6 and NH 4ClO 4

Abstract

Deuteron spin–lattice relaxation is studied in 5% and 100% deuterated ammonium hexachlorostannate and perchlorate. The relaxation rate is observed to be independent of deuteration down to temperatures slightly lower than that of the maximum. At lower temperatures the rate of the 5% deuterated sample exceeds that of the 100% deuterated sample by four and two orders of magnitude in ammonium hexachlorostannate and perchlorate, respectively. The angular dependence of the deuteron relaxation rate in 5% deuterated ammonium hexachlorostannate at 6 K is explained in terms of existing models on quadrupolar relaxation. In 5% ammonium perchlorate one hydrogen equilibrium position, which lies on the preferred axis for 120° rotations, has a larger probability to be occupied by the deuteron of NH 3D + ions. The deuterons at the other positions are still performing rotational jumps about the preferred C 3 axis and also about the other threefold axes, although at a slower rate. Such observations require a reconsideration of the relaxation process. A somewhat more general expression is derived for the relaxation rate, which agrees with the experimentally observed angular dependence for 5% deuterated ammonium perchlorate at 60 K. At lower temperatures the quadrupole coupling of the deuterons at the preferred axis may become practically time-independent. Then a significant contribution to the relaxation rate can be provided by the deuteron–proton magnetic dipolar interaction, which is still fluctuating fast via the rotation of the three protons about the axis through the stationary deuteron.