We report on infrared, Raman, magnetic susceptibility, and specific heat measurements on CdCr2O4 and ZnCr2O4 single crystals. We estimate the nearest-neighbor and next-nearest neighbor exchange constants from the magnetic susceptibility and extract t
he spin-spin correlation functions obtained from the magnetic susceptibility and the magnetic contribution to the specific heat. By comparing with the frequency shift of the infrared optical phonons above TN , we derive estimates for the spin-phonon coupling constants in these systems. The observation of phonon modes which are both Raman and infrared active suggest the loss of inversion symmetry below the Neel temperature in CdCr2O4 in agreement with theoretical predictions by Chern and coworkers [Phys. Rev. B 74, 060405 (2006)]. In ZnCr2O4 several new modes appear below TN, but no phonon modes could be detected which are both Raman and infrared active indicating the conservation of inversion symmetry in the low temperature phase.
The reflectivity of single-crystalline CoO has been studied by optical spectroscopy for wave numbers ranging from 100 to 28,000wn and for temperatures 8 $< T <$ 325 K@. A splitting of the cubic IR-active phonon mode on passing the antiferromagnetic p
hase transition at $T_N$ = 289 K has been observed. At low temperatures the splitting amounts to 15.0wn. In addition, we studied the splitting of the cubic crystal field ground state of the Co$^{2+}$ ions due to spin-orbit coupling, a tetragonal crystal field, and exchange interaction. Below $T_N$, magnetic dipole transitions between the exchange-split levels are identified and the energy-level scheme can be well described with a spin-orbit coupling $lambda = 151.1wn$, an exchange constant $J = 17.5wn$, and a tetragonal crystal-field parameter $D = -47.8wn$. Already in the paramagnetic state electric quadrupole transitions between the spin-orbit split level have been observed. At high frequencies, two electronic levels of the crystal-field-split $d$-manifold were identified at 8,000 and 18,500wn.
We report on phonon properties and electronic transitions in CaCu3Ti4O12, a material which reveals a colossal dielectric constant at room temperature without any ferroelectric transition. The results of far- and mid-infrared measurements are compared
to those obtained by broadband dielectric and millimeter-wave spectroscopy on the same single crystal. The unusual temperature dependence of phonon eigenfrequencies, dampings and ionic plasma frequencies of low lying phonon modes are analyzed and discussed in detail. Electronic excitations below 4 eV are identified as transitions between full and empty hybridized oxygen-copper bands and between oxygen-copper and unoccupied Ti 3d bands. The unusually small band gap determined from the dc-conductivity (~200 meV) compares well with the optical results.
Polar phonons of HgCr2S4 and CdCr2S4 are studied by far-infrared spectroscopy as a function of temperature and external magnetic field. Eigenfrequencies, damping constants, effective plasma frequencies and Lyddane-Sachs-Teller relations, and effectiv
e charges are determined. Ferromagnetic CdCr2S4 and antiferromagnetic HgCr2S4 behave rather similar. Both compounds are dominated by ferromagnetic exchange and although HgCr2S4 is an antiferromagnet, no phonon splitting can be observed at the magnetic phase transition. Temperature and magnetic field dependence of the eigenfrequencies show no anomalies indicating displacive polar soft mode behavior. However, significant effects are detected in the temperature dependence of the plasma frequencies indicating changes in the nature of the bonds and significant charge transfer. In HgCr2S4 we provide experimental evidence that the magnetic field dependence of specific polar modes reveal shifts exactly correlated with the magnetization showing significant magneto-dielectric effects even at infrared frequencies.
