Optical properties and electronic structure of rare-earth ferroborates

The optical absorption spectra of single-crystal ferroborate GdFe₃(BO₃)₄ and GdFe_2.1Ga_0.9(BO₃)₄ are measured and interpreted. It is found that the absorption edge and the absorption bands A, B, and C observed below the edge are close to those for FeBO₃. A many-electron model of the band structure of GdFe₃(BO₃)₄ is suggested including strong electron correlations between the iron d states. It is shown that GdFe₃(BO₃)₄ has a charge-transfer dielectric gap. A rise in pressure is predicted to result in a crossover between the high-spin and low-spin states of the Fe³⁺ ion, collapse of the magnetic moment, a weakening of Coulomb correlations, an abrupt reduction in the energy gap, and an insulator-semiconductor transition.