Theoretical structure and surface energy of the reconstructed {01.2} form of calcite (CaCO3) crystal

Two different reconstructions of the (01.2) face (Ca or CO₃ terminated) of calcite (CaCO₃) were studied: (i) R1 reconstruction: the outermost layer is based on the 0 1 0] × 1/32 1 1] rectangular mesh, which is symmetrical with respect to the c glide plane of the crystal, thus fulfilling the 2D symmetry of the face and (ii) R2 reconstruction: the outermost layer is based on a lozenge shaped mesh that does not respect the 2D symmetry of the face.The , , and slabs geometry optimizations of calcite (CaCO₃) were performed either at DFT level or by using empirical potentials; the results obtained with these two different calculation methodologies are in good agreement. With respect to their arrangement in the bulk, the CO₃ groups of the outermost layer are significantly rotated about the crystallographic a-axis and about the normal to the 01.2 plane; further, the thickness of the outermost layer is significantly lower than that of the underneath ones.The surfaces energies (γ) at 0 K, for relaxed and unrelaxed , , and faces, were determined either at DFT level or by using empirical potentials. Independently of the method of calculation employed, the stability order of the relaxed faces is < < < . Concerning the unrelaxed faces, whose energies were evaluated by using empirical potentials only, the stability order is instead < < < ; such different ordering shows the importance of geometry relaxation in the calculation of the surface energy. The values of the relaxed surface energies are , , and erg/cm².