Raman spectroscopy of alpha-FeOOH (goethite) near antiferromagnetic to paramagnetic phase transition

Synthetic powder, ore samples, and mineral single crystals of goethite ( alpha -FeOOH) were investigated with polarized Raman spectroscopy at temperatures from 293K to 473K. The symmetry of the vibrational modes, observed in different scattering configurations, was determined unequivocally. The assignment of the Raman-active modes to definite atomic vibrations is supported by two types of lattice-dynamical calculations: empirical shell model and ab initio density functional theory. The temperature dependencies of the line shape parameters of some Raman-active vibrations at temperatures near to the antiferromagnetic-paramagnetic phase transition infers for a significant spin-lattice coupling in this compound. The most informative in this aspect is the B 3 g phonon at 387 mml:mspace width=".1em"mml:mspace cm - 1, which overlays a broad scattering background and displays a pronounced asymmetric Fano-line shape. The asymmetry increases in the paramagnetic state above the Neel temperature ( T N = 393 mml:mspace width=".1em"mml:mspace K), indicating a strong interaction of this mode with the underlying excitation continuum. The origin of the excitation background is discussed in light of our experimental results and the existing data for the magnetic structure and transport properties of alpha -FeOOH. By using the molecular-orbital dimer approach, we calculate the spin-phonon coupling constants for the B 3 g mode as J ' = - 0.2 mml:mspace width=".1em"mml:mspace eV / angstrom and J '' = + 0.18 <mml:mspace width=".1em"mml:mspace eV / angstrom 2, respectively. Thus, we rationalize that, most probably, the scattering background stems from magnetic excitations, and the asymmetric shape of the B 3 g band is a result of a linear spin-phonon coupling of this mode with the Fe-O1-Fe spin dimers. Another mechanism, a phonon interaction with thermally activated charge carriers above T N, is also considered.