Far-infrared reflection spectra, TO- and LO-phonon frequencies, coupled and decoupled plasmon-phonon modes, dielectric constants, and effective dynamical charges of manganese, iron, and platinum group pyrite type compounds

Abstract

The far-infrared reflection spectra of hot-pressed samples of the pyrites MX 2 with M = Mn, Fe, Ru, and Os and X = S, Se, and Te and PtY 2 with Y = P, As, and Sb are presented in the range from 40 to 700 cm −1. The spectra show five reststrahlen bands and more or less free carrier contributions due to deviation from stoichiometry. The oscillator parameters ω j , ρ j , γ j , ω p, and γ o, the transverse optical phonon frequencies ω TO, and the coupled plasmon-phonon frequencies Ω + and Ω − were calculated. The uncoupled longitudinal optical phonon frequencies ω LO were determined from −Im ( 1 \\ ̂ ge ) of the plasmon-free phonon spectra calculated from the oscillator parameters, neglecting the free carrier contributions. The obtained effective ionic charges (Szigeti charges) reveal an increasing covalency of the pyrites in the order pnictides > chalcides and Fe > Ru > Os > Mn compounds. The phonon frequencies reflect the increasing bond strengths on going from 3 d to 4 d and 5 d metal compounds, discussed in a former work ( Phys. Chem. Miner. 9, 109 (1983)). The true intensities of the phonon modes for using them with respect to lattice dynamical calculations are discussed.