Deuteron NMR spectra of ND4ClO4 single crystal at low temperatures.
2H NMR spectra of ND4ClO4 single crystal were obtained at v0 = 44 MHz. Orientation and temperature (1.9-75 K) dependences were measured. Fitting the spectra gives the effective quadrupole coupling constants for all deuterons and the ground torsional level structure. The isotope reduction of the (A-T) and (A-E) tunnelling splittings, i.e., the ratios of the respective splittings for NH4+ and ND4+, were found to be different. The splittings at T = 24 K are about 60% of the helium temperature values. The spectrum undergoes intermediate narrowing by reorientations between 26 and 34 K and tunnelling related features in the spectra are eradicated. After reaching the extreme narrowing limit, a doublet with gradually decreasing separation was observed, what was attributed to averaging by torsional oscillations of increasing amplitude. At high temperatures (T > 75 K), the narrow spectrum reflects fast multiaxial reorientation of the ammonium ion.
Proton magnetic resonance studies of quantum mechanical tunnelling of ammonium ions in several ammonium salts
Proton magnetic resonance spectra were measured at 1·8 K for the compounds NH4Br, NH4I, NH4SCN, (NH4)2CrO4, and NH4NO3. The observed derivative curves cannot be explained on the basis only of the dipolar interactions between protons in the NH4 + ion held rigidly in the crystal lattices. We considered the effect of quantum mechanical tunnelling on the rotation of an NH4 + ion about its C3-axis and calculated the theoretical lineshapes for various assumed values of the tunnelling splitting constants. Comparison between experiment and theory is quite satisfactory, and the tunnelling splitting constants, Δ, in the librational ground state of the ammonium ion in these salts are determined. It is found that there is a linear relation between the Δ values and the potential barrier to reorientation.
NMR lineshapes of ammonium ions undergoing quantum mechanical tunnelling in the solid state at low temperatures
Abstract Calculations have been made of the 1H NMR powder lineshape of ammonium ions undergoing quantum mechanical tunnelling through the potential barrier to reorientation in the solid state. Theoretical lineshapes have been obtained as a function of the tunnelling spitting and are compared to spectra observed by us and to previously observed (but unexplained) spectra. Agreement between the experimental and the calculated spectra is good in many of the cases studied.