Charge fluctuations and ethylene-group-ordering transition in β''-(BEDT-TTF)4[(H3O)Fe(C2O4)3]⋅Y molecular charge-transfer salts

The polarized infrared reflectance and Raman spectra of the three quasi-two-dimensional β''-(BEDT-TTF)4[(H3O)Fe(C2O4)3]⋅Y bifunctional charge-transfer salts, where BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene and Y = C6H5Br, (C6H5CN)0.17(C6H5Br)0.83, (C6H5CN)0.4(C6H5F)0.6, have been measured as a function of the temperature. Signatures of charge inhomogenity have been found in both Raman and infrared spectra of the β''-(BEDT-TTF)4[(H3O)Fe(C2O4)3]⋅Y superconductors. A 100 K transition to a mixed insulating/metallic state is clearly seen for the first time in the temperature dependence of the electronic spectra of superconducting β''-(BEDT-TTF)4[(H3O)Fe(C2O4)3]⋅C6H5Br. We suggest that this phase transition is due to subtle changes in the ethylene groups ordering, which are related to a structural phase transition in the anionic layer. The infrared and Raman spectra of quasi-two-dimensional metal α-'pseudo-κ'-(BEDT-TTF)4[(H3O)Fe(C2O4)3]C6H4Br2 are also investigated.