Charge-density analysis of spodumene (LiAlSi2O6), from ab initio Hartree?Fock calculations

Abstract

An ab initio Hartree–Fock study of spodumene structure has been performed, and the wave function was used for a topological analysis of the electron density. The three non-equivalent oxygen atoms (O1, O2 and O3) of spodumene differed mainly in their valence shell charge concentration (VSCC). In particular, O1 shows a maximum of charge concentration along the Si–O bond path, and two other maxima, which can be regarded as lone pairs, point in the opposite direction with respect to the silicon position. O2 shows a torus of local charge concentration, whose axis is parallel to the Al–Si direction, with a bulge on the external side of the Si–O2–Al angle; even if no maximum exists in the Si direction, the valence shell of O2 appears to be strongly polarized toward the silicon; a slight polarization also exists along the Al–O bond path. A similar situation is displayed by O3, whose charge concentration has a torus-like shape, with the axis parallel to the Si–Si direction, and a bulge on the external side of the Si–O3–Si angle; as in the case of O2, a significant polarization of the valence shell of O3 is observed, towards the two Si directions. By recasting the calculated electron distribution in terms of the valence bond theory, a correlation has been found between structural details (bond lengths) and the hybridization state of the oxygen atoms.