The pressure dependence of the first-order Raman peak and two second-order Raman features of ThO₂ crystallizing in the fluorite-type structure is investigated using a diamond anvil cell, up to 40GPa. A phase transition from the fluorite phase is observed near 30 GPa as evidenced by the appearance of seven new Raman peaks. The high pressure phases of ThO₂ and CeO₂ exhibit similar Raman features and from this it is believed that the two structures are the same, and have the PbCl₂-type structure. The pressure dependence dω/dP of the observed phonons and their mode Grüneisen parameters are similar to the isostructural CeO₂. The observed second-order Raman features are also identified from the calculated phonon dispersion curves for ThO₂.

Hydrostatic pressure has been used to tune in resonance Raman scattering (RRS) in bulk GaAs. Using a diamond anvil cell, both the photoluminescence peak (PL) and the 2 LO and LO-phonon Raman scattered intensities have been monitored, to establish RRS conditions. When theE₀ gap of GaAs matchesħω_S orħω_L, the 2 LO and LO-phonon intensity, respectively, exhibit resonance Raman scattering maxima, at pressures determined byħω_L. With 647.1 nm radiation (ħω_L = 1.916 eV), a sharp and narrow resonance peak at 3.75 GPa is observed for the 2 LO-phonon. At this pressure the 2 LO-phonon goes through its maximum intensity, and falls right on top of the PL peak, revealing thatħω_S(2 LO) =E₀. This is the condition for “outgoing” resonance. Experiments with other excitation energies (ħω_L) show, that the 2 LO resonance peak-pressure moves to higher pressure with increasingħω_L, and the shift follows precisely theE₀ gap. Thus, the 2 LO RRS is an excellent probe to follow theE₀ gap, far beyond the Γ-X cross-over point. A brief discussion of the theoretical expression for resonance Raman cross section is given, and from this the possibility of a double resonance condition for the observed 2 LO resonance is suggested. The LO-phonon resonance occurs at a pressure whenħω_L ≈E₀, but the pressure-induced transparency of the GaAs masks the true resonance profile.

The effect of pressure on the Raman modes in TeO₂ (paratellurite) has been investigated to 30GPa, using the diamond cell and argon as pressure medium. The pressure dependence of the Raman modes indicates four pressure-induced phase transitions near 1 GPa, 4.5 GPa, 11 GPa and 22 GPa. Of these the first is the well studied second-order transition fromD₄⁴ symmetry toD₂⁴ symmetry, driven by a soft acoustic shear mode instability. The remarkable similarity in the Raman spectra of phases I to IV suggest that only subtle changes in the structure are involved in these phase transitions. The totally different Raman spectral features of phase V indicate major structural changes at the 22GPa transition. It is suggested that this high pressure-phase is similar to PbCl₂-type, from high pressure crystal chemical considerations. The need for a high pressure X-ray diffraction study on TeO₂ is emphasized, to unravel the structure of the various high pressure phases in the system.