W. H. Qi

Quantum-mechanical model for estimating the number ratio between different valence cations in multiatom compounds

A quantum-mechanical potential barrier model for estimating the number ratio between different valence cations in multiatom compounds is proposed. It is supposed that there is a potential barrier between a cation-anion pair. The height of the potential barrier is proportional to the ionization energy of the cation, and the width of the potential barrier is related to the distance between neighboring cations and anions. As examples for using this model, the distribution of cations with different valences in some ABO3 lanthanum manganites is explained satisfactorily.

Quantum-mechanical method for estimating ion distributions in spinel ferrites

A quantum-mechanical method for estimating the cation distribution in spinel ferrites is proposed, by which the ionization energy of the cations and the Pauli repulsion energy is considered, together with the magnetic ordered energy and the tendency toward charge density balance. Using this method, not only can the difference between the observed and the traditional theoretical magnetic moments of the spinel structure ferrites MFe2O4 (M=Mn,Fe,Co,Ni,Cu) be explained, but also the dependence of the magnetic moments of the ferrites M1−xZnxFe2O4 (M=Mn,Fe,Co,Ni,Cu) on the doping level x can be fitted.

Rietveld fitting of x-ray diffraction spectra for the double phase composites La0.7−xSr0.3Mn1−yO3−1.5(x+y)/(Mn3O4)y/3

The effects of lanthanum deficiency on the structural and magnetic properties of manganites with normal composition La0.7−xSr0.3MnO3 prepared by the sol-gel method with the highest heat treatment temperature at 800u2009°C have been investigated. X-ray diffraction (XRD) spectra indicate that the materials possess a single phase with the R3¯c perovskite structure for x≤0.05, and that they possess two phases with the R3¯c perovskite being the dominant phase and Mn3O4 being the second phase for x≥0.10. Using XRD analysis, these materials can be expressed as La0.7−xSr0.3Mn1−yO3−1.5(x+y)/(Mn3O4)y/3. On the basis of the thermal equilibrium theory of crystal defects, the ion ratios at the A, B, and O sites in the ABO3 perovskite phase were calculated. Those ion ratios were used in Rietveld fitting of the XRD spectra. It was found that the dependence of the Curie temperature TC on the content ratio RM4 of Mn4+ ions at B site is similar to that of the typical perovskite La1−xSrxMnO3.

Influence of cohesive energy on unit cell volume of perovskite manganites La1−xMxMnO3

Ionic size is considered to be an important factor influencing the unit cell volume of manganites with an ABO3 structure. For La1−xSrxMnO3, however, although the average effective ion radius of all cations taken together increases with increasing x, the unit cell volume decreases for x<0.5. In the case of La1−xNaxMnO3, the unit cell volume reaches a minimum when x=0.3. Up to now, no satisfactory explanation of these phenomena has been found. In this letter, an explanation based on the ionic cohesive energy with a small additional metallic cohesive energy is described.

Study of the free energy of the La1−xCaxMnO3 manganites based on the temperature dependence of the crystal cell volume

A study of the free energy of the perovskite manganites was performed by fitting experimental results for the temperature dependence of the crystal cell volume using a detailed semiclassical model of the free energy. The fitted results coincide with the experimental results for the samples La1−xCaxMnO3 (x=0.2, 0.25, 0.3, and 0.5). The free energy includes the energy corresponding to thermal vibration of the crystal lattice, the ionic cohesive energy, and additional energies produced by electrical carriers from the double exchange mechanism and the thermal activation of small polarons.