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77 - S. Frank , A. Huber , U. Ammerahl 2014
We present a polarization-dependent infrared reflectivity study of the spin-ladder compound Sr$_{2.5}$Ca$_{11.5}$Cu$_{24}$O$_{41}$ under pressure. The optical response is strongly anisotropic, with the highest reflectivity along the ladders/chains (t extbf{E}$|$c) revealing a metallic character. For the polarization direction perpendicular to the ladder plane, an insulating behavior is observed. With increasing pressure the optical conductivity for textbf{E}$|$c shows a strong increase, which is most pronounced below 2000~cm$^{-1}$. According to the spectral weight analysis of the textbf{E}$|$c optical conductivity the hole concentration in the ladders increases with increasing pressure and tends to saturate at high pressure. At $sim$7.5~GPa the number of holes per Cu atom in the ladders has increased by $Delta delta$=0.09 ($pm$0.01), and the Cu valence in the ladders has reached the value +2.33. The optical data suggest that Sr$_{2.5}$Ca$_{11.5}$Cu$_{24}$O$_{41}$ remains electronically highly anisotropic up to high pressure, also at low temperatures.
We report pressure-dependent reflection and transmission measurements on ZnCr$_2$Se$_4$, HgCr$_2$S$_4$, and CdCr$_2$O$_4$ single crystals at room temperature over a broad spectral range 200-24000 cm$^{-1}$. The pressure dependence of the phonon modes and the high-frequency electronic excitations indicates that all three compounds undergo a pressure-induced structural phase transition with the critical pressure 15 GPa, 12 GPa, and 10 GPa for CdCr$_2$O$_4$, HgCr$_2$S$_4$, and ZnCr$_2$Se$_4$, respectively. The eigenfrequencies of the electronic transitions are very close to the expected values for chromium crystal-field transitions. In the case of the chalcogenides pressure induces a red shift of the electronic excitation which indicates a strong hybridization of the Cr d-bands with the chalcogenide bands.
We investigated the electronic and vibrational properties of magnetite at temperatures from 300 K down to 10 K and for pressures up to 10 GPa by far-infrared reflectivity measurements. The Verwey transition is manifested by a drastic decrease of the overall reflectance and the splitting of the phonon modes as well as the activation of additional phonon modes. In the whole studied pressure range the down-shift of the overall reflectance spectrum saturates and the maximum number of phonon modes is reached at a critical temperature, which sets a lower bound for the Verwey transition temperature T$_{mathrm{v}}$. Based on these optical results a pressure-temperature phase diagram for magnetite is proposed.
The optical properties of magnetite at room temperature were studied by infrared reflectivity measurements as a function of pressure up to 8 GPa. The optical conductivity spectrum consists of a Drude term, two sharp phonon modes, a far-infrared band at around 600 cm$^{-1}$, and a pronounced mid-infrared absorption band. With increasing pressure both absorption bands shift to lower frequencies and the phonon modes harden in a linear fashion. Based on the shape of the MIR band, the temperature dependence of the dc transport data, and the occurrence of the far-infrared band in the optical conductivity spectrum the polaronic coupling strength in magnetite at room temperature should be classified as intermediate. For the lower-energy phonon mode an abrupt increase of the linear pressure coefficient occurs at around 6 GPa, which could be attributed to minor alterations of the charge distribution among the different Fe sites.
The electronic properties of as-prepared and purified unoriented single-walled carbon nanotube films were studied by transmission measurements over a broad frequency range (far-infrared up to visible) as a function of temperature (15 K - 295 K) and e xternal pressure (up to 8 GPa). Both the as-prepared and the purified SWCNT films exhibit nearly temperature-independent properties. With increasing pressure the low-energy absorbance decreases suggesting an increasing carrier localization due to pressure-induced deformations. The energy of the optical transitions in the SWCNTs decreases with increasing pressure, which can be attributed to pressure-induced hybridization and symmetry-breaking effects. We find an anomaly in the pressure-induced shift of the optical transitions at $sim$2 GPa due to a structural phase transition.
Pressure-dependent transmittance and reflectance spectra of TiOBr and TiOCl single crystals at room temperature suggest the closure of the Mott-Hubbard gap, i.e., the gap is filled with additional electronic states extending down to the far-infrared range. According to pressure-dependent x-ray powder diffraction data the gap closure coincides with a structural phase transition. The transition in TiOBr occurs at slightly lower pressure ($p$=14 GPa) compared to TiOCl ($p$=16 GPa) under hydrostatic conditions, which is discussed in terms of the chemical pressure effect. The results of pressure-dependent transmittance measurements on TiOBr at low temperatures reveal similar effects at 23 K, where the compound is in the spin-Peierls phase at ambient pressure.
We investigated the pressure-dependent optical response of the low-dimensional Mott-Hubbard insulator TiOBr by transmittance and reflectance measurements in the infrared and visible frequency range. A suppression of the transmittance above a critical pressure and a concomitant increase of the reflectance are observed, suggesting a pressure-induced metallization of TiOBr. The metallic phase of TiOBr at high pressure is confirmed by the presence of additional excitations extending down to the far-infrared range. The pressure-induced metallization coincides with a structural phase transition, according to the results of x-ray powder diffraction experiments under pressure.
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