The heat capacity of orientationally disordered solid solutions (CH4)nKr1−n (n=75 and 78 mole% CH4 in the temperature interval ΔT=0.8–20 K) and (CD4)nKr1−n (n=50, 60, and 70 mole% CD4, ΔT=0.6–30 K) is investigated. At liquid-helium temperatures the temperature dependences of the molar heat capacities of the rotational subsystems of the solutions are qualitatively and quantitatively very different. One of the main reasons for the effect is that in the concentrated solutions investigated the CD4 molecules are in a substantially stronger molecular field than the CH4 molecules. This is because in low-energy states the effective octupole electric moment of CD4 molecules, which determines the molecular field, is larger than the effective octupole moment of the more quantum molecules CH4. The weak concentration dependences of the heat capacity of the solutions studied are due to the influence of frustration, which weakens the molecular fields produced at the lattice sites by the surrounding molecules. No evidence of the formation of orientational octupole glasses in the experimental systems was found.
The heat capacity of Kr–nCH4 solid solutions with the concentrations n=1; 5; 10% and of the solid solution Kr–1% CH4–0.2% O2 is studied at 0.7–8 K. The contributions Crot to the heat capacity of the solutions due to the rotation of the CH4 molecules are estimated. The deviations of the measured Crot from the values corresponding to the equilibrium distribution of the CH4 nuclear spin modifications are dependent on the correlation between the characteristic times of conversion and of the calorimetric experiment. The effects of temperature, O2 impurities, and CH4 clusters upon the conversion rate are studied. It is shown that the hybrid mechanism of conversion proposed by Berlinsky and Nijman, which takes into account both intramolecular and intermolecular interactions of the proton spins, is predominant.
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