First-principles modeling of the infrared spectrum of Fe- A nd Al-bearing lizardite

Abstract

The theoretical vibrational properties of a series of Fe- A nd Al-bearing lizardite models have been determined at the density functional theory level. Each periodic model displays a single cationic impurity substituted at an octahedral or tetrahedral site of a supercell of lizardite (Mg3Si2O5(OH)4) containing 162 atoms. The isovalent Fe2+ for Mg2+ substitution has been considered, as well as the heterovalent substitution of Fe3+ or Al3+ for Mg2+ or Si4+. Comparison of the theoretical absorption spectra with previously reported experimental spectra of natural and laboratory-grown lizardite samples allows us to propose an interpretation for most of the observed bands. Although the identification of specific bands related to octahedral Fe2+ in FTIR spectra is challenging, broad bands at 3584 and 3566 cm-1 reflect the occurrence of octahedral Al3+ and Fe3+, respectively, in the natural samples. These broad bands likely overlap with potential contribution related to tetrahedral Al3+. It is suggested that the modification of the H-bonding pattern related to the incorporation of trivalent ions at tetrahedral sites has an overall broadening effect on the interlayer-OH stretching bands of lizardite.