Quantum effects in the low temperature reorientation of N 2− in KCl and KI

Abstract

The electron paramagnetic resonance (EPR) spectra of KCl:N 2 − and KI:N 2 − were studied as a function of temperature and applied uniaxial stress in the temperature range 2–35°K. The molecular reorientation rates were determined for both 60 and 90° reorientations from the motional broadening and narrowing effects in the observed spectra. Although thermally activated in the range 15–35°K for KCl:N 2 −, the parameters deduced from the data are not consistent with a simple classical model of the motion. In both hosts the 90° rotation is markedly faster than the 60° reorientation, in conflict with simple models, but explicable in terms of the suppression of the tunneling matrix elements by polarization of the host crystal. In KI:N 2 −, the 90° reorientation is still apparent at 1·7°K and the spectra clearly show the influence of the symmetry of the nuclear spin states upon the reorientation kinetics, an effect predicted by Sussman.