Ab initio quantum-mechanical modeling of pyrophyllite [Al2Si4O10(OH)(2)] and talc [Mg3Si4O10(OH)(2)] surfaces

摘要

Bulk and slab geometry optimizations and calculations of the electrostatic potential at the surface of both pyrophyllite [Al2Si4O10(OH)(2)] and talc [Mg3Si4O10(OH)(2)] were performed at Hartree - Fock and DFT level. In both pyrophyllite and talc cases, a modest ( 001) surface relaxation was observed, and the surface preserves the structural features of the crystal: in the case of pyrophyllite the tetrahedral and octahedral sheets are strongly distorted with respect to the ideal hexagonal symmetry ( and basal oxygen are located at different heights along the direction normal to the basal plane), whereas the structure of talc deviates slightly from the ideal hexagonal symmetry ( almost co-planar basal oxygen). The calculated distortions are fully consistent with those experimentally observed. Although the potentials at the surface of pyrophyllite and talc are of the same order of magnitude, large topological differences were observed, which could possibly be ascribed to the differences between the surface structures of the two minerals. Negative values of the potential are located above the basal oxygen and at the center of the tetrahedral ring; above silicon the potential is always positive. The value of the potential minimum above the center of the tetrahedral ring of pyrophyllite is - 0.05 V ( at 2 angstrom from the surface), whereas in the case of talc the minimum is - 0.01 V, at 2.7 angstrom. In the case of pyrophyllite the minimum of potential above the higher basal oxygen is located at 1.1 angstrom and it has a value of - 1.25 V, whereas above the lower oxygen the value of the potential at the minimum is - 0.2 V, at 1.25 angstrom; the talc exhibits a minimum of - 0.75 V at 1.2 angstrom, above the basal oxygen.