GEOPHYSICS, ASTRONOMY, AND ASTROPHYSICS: Theoretical Studies on Defects of Kaolinite in Clays

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Using the first-principles methods, we study the formation energetics and charge doping properties of the extrinsic substitutional defects in kaolinite. Especially, we choose Be, Mg, Ca, Fe, Cr, Mn, Cu, Zn as extrinsic defects to substitute for Al atoms. By systematically calculating the impurity formation energies and transition energy levels, we find that all group-II defects introduce the relative shallow transition energy levels in kaolinite. Among them, MgAl has the shallowest transition energy level at 0.08 eV above the valence band maximum. The transition-elemental defects FeAl, CrAl, and MnAl are found to have relative low formation energies, suggesting their easy formation in kaolinite under natural surrounding conditions. Our calculations show that the defects CuAl and ZnAl have the high formation energies and deep transition energy levels, which exclude the possibility of their formation in natural kaolinite.

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