Interpretation of the Magnetic Properties of LaCoO3

Abstract
Susceptibility measurements have been carried out on single‐crystal LaCoO3 in the temperature range of 4.2° to 300°K. We find an effective magnetic moment squared that agrees with Heikes et al. at 300°K, but which falls more rapidly with decreasing temperature. Paramagnetic resonance measurements at 4.2°, 77°, and 300°K have ruled out the presence of modest quantities of paramagnetic cobalt, leaving only the possibilities of diamagnetic or highly concentrated paramagnetic Co+3. (Large concentrations of other cobalt valencies are ruled out for chemical reasons.) Using a model found successful by Goodenough, we assume that Co+3 is near the crossover point, with the 1A1 state lowest. A calculation including spin‐orbit effects, but assuming cubic symmetry for the 300° to 4.2°K range, gives essentially a linear variation for the energy difference between the 1A1 and the center of gravity of the 5T2 states, opposite to that expected for a cubic variation. This effect can be explained by including a lower symmetry distortion (probably trigonal) which increases with decreasing temperature, similar to that found in LaAlO3:Cr.