MOLECULAR REORIENTATION AND NUCLEAR-SPIN CONVERSION IN SOLID DEUTEROMETHANES AT LOW TEMPERATURES

The heat capacities of the solid deuteromethanes have been measured down to 0.3°K, tracing out the low-temperature heat-capacity anomalies which had been detected in the earlier work of Colwell, Gill, and Morrison. The anomalies in CH3D and CHD3 have maxima at 0.43 and 0.48°K, respectively, but the CH2D2 heat capacity is still increasing with decreasing temperature at 0.3°K. A small anomaly was found in CD4 but this is ascribed to chemical and isotopic impurities present in the sample. The heatcapacity anomalies are of the Schottky form and are believed to arise from the reorientation of the molecules on the lattice sites. This results in the removal of the orientational degeneracies of the molecules which give rise to the zero-point entropies of R In4 for CH3D and CHD3 and R In6 for CH2D2. In molecules having identical protons, conversion between the different nuclear-spin states also occurs. This is substantiated in the case of CH 3D where the measured entropy change in the range of the measurements, 0.3-44.0°K, is ΔS = 1.614R, which exceeds the maximum value of R In4 (1.386R) for molecular reorientation occurring separately. The occurrence of conversion was also indicated by a thermal relaxation process characterized by relaxation times ranging from 110 to 50 sec in going from 0.3 to 4.0°K. Analysis of the CH2D2 data indicates that nuclear-spin conversion is also taking place in this material but the result is less well established. There is no indication of conversion occurring in CHD3 Reasonably precise values of the energylevel splittings have been derived for each of the partially deuterated methanes.